Diamonds coatings and methods of making and using the same

ABSTRACT

Disclosed herein are chemically configurable diamonds tailored for self-cleaning, dirt repelling, and anti-smudge technology for sensing, optical, and ornamental applications. This document describes an invention for generating chemically configurable diamonds. Applications include anti-smudge, self-cleaning, color alteration, and debris resistance for diamond for jewelry or other ornamentation, optical, quantum computing, for chemical functionalization for sensors or electronic devices that rely on chemical interactions with diamonds or defects therein. Diamond surfaces are chemically inert and therefore require chemical modification to attach secondary coatings. Secondary coatings can be varied depending on application demands. Chemical reactions are employed to modify the surface wetting properties of the diamond. The wetting properties of the diamond can lend a hydrophilic, hydrophobic, lipophobic, or lipophilic effect to the diamond, or include explicit chemical functionality, depending on the nature of the coating, and tailored to the desired application. The coated diamond is constructed by fabricating a functional base layer on the diamond and subsequently attaching the desired chemical monolayer or multilayer to that base.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of PCT Application No.PCT/US2022/014917, filed Feb. 2, 2022, and claims the benefit of U.S.Provisional Application No. 63/145,821, filed Feb. 4, 2021, which areincorporated in their entirety herein by reference.

FIELD

This disclosure relates generally to coatings for different articles,such as jewelry (e.g., diamonds), lenses (e.g., for glasses, sunglasses,magnifying lenses, etc.), or other goods and methods for making andusing the same. The coatings resist oil, dirt, and grime build-up.

BACKGROUND Description of the Related Art

Over time, gemstone surfaces (e.g., the surface of a diamond or othergemstone), can attract dirt and grime. Dirt and grime can dull theappearance of the gemstone.

SUMMARY

The highly non-reactive, hydrophobic hydrocarbon surface of a diamondattracts oil and grime. Thus, diamond surfaces become soiled quicklyafter cleaning. This soiling causes diamonds to lose their brilliance,luster, and fire, making them less attractive to wearers. Diamondbrilliance creates the white sparkle of a diamond. It makes it seem likelight is pouring out of the diamond. Diamond fire causes the rainbowcolored sparkle some diamonds may have. The reflection of white lightinside a diamond is diamond brilliance. Diamond fire is the diffractionof white light into a rainbow of colors. It's similar to how a rainbowis formed after a rainstorm. Soiling causes a loss of these and otherbeneficial properties of diamonds.

The non-reactive surface of diamonds also make them particularlydifficult to functionalize. For instance, while silane chemistry is apotential avenue to introduce anti-soiling properties to the surface ofa jewelry diamond, the diamond surface is not reactive enough tocovalently couple sufficiently to silanes to allow effective coating.While silanes can be used to prepare monolayers on surfaces such asglass and plastic, the covalent bonding of a silane to a surfacerequires the surface be regular and nucleophilic. The nucleophilicgroups on the surface displace leaving groups on the silane atom,bonding the silane to the surface. While this process is practical forfunctionalizing surfaces having nucleophiles already present, onsurfaces that lack nucleophilic groups (or lack a sufficient density oramount of nucleophilic groups), silanization cannot be accomplished toan appreciable, effective, and/or useable degree. In the case ofgemstones, such as diamond, the surface lacks sufficient reactivity toprovide regular and dense silanization (and coating formation). Alsoproblematic is the expense associated with jewelry grade diamonds.Because jewelry grade diamonds are expensive, scientists have beenreluctant to diamonds to processing and/or functionalizing conditions.

Disclosed herein are methods of covalently coating substrate surfaces(e.g., gemstone surfaces, especially diamond surfaces, etc.) withsilanes. Some embodiments disclosed herein solve the above problemsand/or other challenges associated with preparing a covalently bonded,anti-soiling layer on a surface (e.g., functionalizing surfaces withsilanes). In several embodiments, a multistep surface preparation isperformed to achieve a surface with sufficient reactivity to alloweffective coating using silane chemistry. Some embodiments pertain tosubstrates having surfaces where high optical quality is desired (e.g.,diamonds, gemstones, lenses, etc.). Some embodiments pertain tosubstrates, such as gems (e.g., diamonds), with a surface comprising asilane having an anti-soiling substituent (e.g., a tail). In severalembodiments, the silane comprises one or more anti-soiling substituents(e.g., tails). In several embodiments, the gem comprises a molecularlycoated surface. In several embodiments, the tail (or tails) of thesilane confer upon the gem anti-soiling properties.

In several embodiments, prior to silanization, the diamond surface (orother surface) is prepared. In several embodiments, the surface isplasma treated. In several embodiments, surprisingly, it has been foundthat plasma treatment and coating of a diamond surface does notsignificantly impact the optical properties of the diamond. That adiamond (or other article) can be plasma treated and coated withoutsignificant loss of optical properties is especially feature issurprising considering that plasma treatment utilizes conditions thatare so harsh that they actually chemically change the surface of thediamond (or other article). In several embodiments, the plasma treatmentis performed using oxygen plasma. In several embodiments, the plasmatreatment is performed using hydrogen plasma. In several embodiments,the plasma treatment may include multiple plasma treatment steps. Forexample, in several embodiments, the plasma treatment process includesexposure to a first type of plasma (e.g., oxygen plasma), followed byexposure to a second type of plasma (e.g., hydrogen plasma).

In several embodiments, the plasma treated surface is annealed usingwater vapor. In several embodiments, surprisingly, it has been foundthat annealing process also does not significantly impact the opticalproperties of the diamond. In several embodiments, after annealing, thediamond is coated with a silane layer (silanized) through reaction witha silanizing group. In several embodiments, the silanizing group (e.g.,which comprises a silane unit) is an alkoxysilane or halosilanecomprising at least one tail group. In several embodiments, the silaneunit comprises an optionally substituted alkyl group as a tail (e.g., ahaloalkyl). In several embodiments, surprisingly, it has been found thatsilanization process also does not significantly impact the opticalproperties of the diamond.

Several embodiments disclosed herein provide a soil resistant surface(e.g., a gemstone surface). In several embodiments, surface is that of agemstone. In several embodiments, the gemstone is a diamond. In severalembodiments, the diamond comprises a jewelry grade diamond gemstonehaving an anti-soiling surface coating. In several embodiments, theanti-soiling surface coating is covalently bonded to the diamond. Inseveral embodiments, the anti-soiling surface coating comprises,consists of, or consists essentially of a monolayer. In severalembodiments, the diamond surface and monolayer is represented by Surface(I):

In several embodiments, n is an integer selected from 0, 1, 2, 3, or 4.In several embodiments, m is an integer ranging from 1 to 15.

Several embodiments pertain to a soil resistant gemstone (e.g., diamond)prepared by a method. Several embodiments pertain to a soil resistantsurface represented by Surface (I) prepared by a method. Severalembodiments pertain to a method of preparing a soil resistant gemstone(e.g., diamond). In several embodiments, the soil resistant diamond isprepared by plasma treating a surface of a raw diamond to provide aprecursor diamond having a precursor diamond surface. In severalembodiments, the precursor diamond surface is chemically different thanthe surface of the raw diamond. In several embodiments, the methodcomprises annealing the precursor diamond to provide a reactive diamondhaving a reactive diamond surface. In several embodiments, the reactivediamond surface is different from the precursor diamond surface. Inseveral embodiments, the method comprises exposing the reactive diamondsurface to a silanizing agent comprising an S-unit. In severalembodiments, each “S-unit” is a silane unit comprising ofSi(CH₂)_(n)(CF₂)_(m)CF₃.

In several embodiments, the surface of the raw diamond compriseshydroxyl groups, carbonyl groups, carboxylic acid groups, epoxidegroups, C—H groups, and C—C groups, as represented in Surface (I-r) bygroups A¹, A², A³, A⁴, A⁵, and A⁶, respectively:

In several embodiments, the a contact angle for water on the surface ofthe raw diamond ranges from 350 to 60°.

In several embodiments, the precursor diamond surface comprises a ratioof A¹ and A⁵ groups relative to a total number of surface groups A¹ toA⁶. In several embodiments, the ratio is quantitatively calculated as(A¹+A⁵)/(A¹+A²+A³+A⁴+A⁵+A⁶). In several embodiments, this ratio isqualitatively calculated (e.g., using FT-IR, FTIR ATR spectroscopy, orother spectroscopic techniques). In several embodiments, the ratio of A¹and A⁵ groups relative to a total number of surface groups A¹ to A⁶ forthe precursor diamond surface is higher than the ratio of A¹ and A⁵groups relative to a total number of surface groups A¹ to A⁶ for the rawdiamond surface. For example, where the ratio of(A¹+A⁵)/(A¹+A²+A³+A⁴+A⁵+A⁶) on the surface of the precursor diamondequals Ratio^(Precusor(1,5)) and where the ratio(A¹+A⁵)/(A¹+A²+A³+A⁴+A⁵+A⁶) on the surface of the raw diamond equalsRatio^(Raw(1,5)), in several embodiments,Ratio^(Precusor(1,5))>Ratio^(Raw(1,5)).

In several embodiments, a contact angle for water on the precursordiamond surface ranges from 300 to 55°.

In several embodiments, the reactive diamond surface comprises a ratioof A¹ groups relative to a total number of surface groups A¹ to A⁶. Inseveral embodiments, the ratio is quantitatively calculated as(A¹)/(A¹+A²+A³+A⁴+A⁵+A⁶). In several embodiments, this ratio isqualitatively calculated (e.g., using FT-IR, FTIR ATR spectroscopy, orother spectroscopic techniques). In several embodiments, the ratio of A¹groups relative to a total number of surface groups A¹ to A⁶ for thereactive diamond surface is higher than the ratio of A¹ groups relativeto a total number of surface groups A¹ to A⁶ for the precursor diamondsurface. For example, where the ratio of (A¹)/(A¹+A²+A³+A⁴+A⁵+A⁶) on thesurface of the precursor diamond equals Ratio^(Reactive(1)) and wherethe ratio (A¹)/(A¹+A²+A³+A⁴+A⁵+A⁶) on the surface of the precursordiamond equals Ratio^(Precursor(1)), in several embodiments,Ratio^(Reactive(1))>Ratio^(Precursor(1)).

In several embodiments, a contact angle for water on the reactivediamond surface ranges from 10° to 40°. In several embodiments, acontact angle for water on the reactive diamond surface ranges from 100to 20°. In several embodiments, a contact angle for water on thereactive diamond surface ranges from 5° to 20°.

In several embodiments, n is 2. In several embodiments, n is 2. Inseveral embodiments, m is between 6 and 12. In several embodiments, m is8.

In several embodiments, each nm² of the soil resistant diamond surfacecomprises equal to or at least 2 S-units.

In several embodiments, the Surface (I) is further represented bySurface (I-i):

In several embodiments, the molecularly coated surface comprises FormulaI:

S-A

T)_(p)   Formula I

where S represents a surface of a gemstone (or another substrate) and-A(-T)_(p) represents the molecular coating; A is an silane or siloxanecovalently bonded to S; T is a pendant moiety (e.g., a tail) bonded toA; p is an integer between 1 and 5; and wherein the coated surface hasdifferent physical properties and/or chemical properties than thesurface prior to coating. In several embodiments, T is 1 or 2. Inseveral embodiments, S is a plasma treated surface. In severalembodiments, A comprises Si (e.g., —Si(O)_(x)— where x is 1, 2, 3, or4). In several embodiments, A-T comprises T-Si(O)_(x)—, where x is 1, 2,or 3, and wherein each O is further bonded to a carbon of the surface orto an adjacent Si (e.g., of an adjacent T-Si(O)_(x)— unit). In severalembodiments, T is an alkyl. In several embodiments, T is optionallysubstituted alkyl. In several embodiments, T is optionally substitutedhaloalkyl. In several embodiments, T is optionally substitutedperflouroalkyl. In several embodiments, T is comprises an optionallysubstituted alkyl portion and an optionally substituted haloalkylportion. In several embodiments, T is an C₁₋₁₀ alkyl (optionallysubstituted) or C₁₋₁₀ perfluoroalkyl (optionally substituted). Inseveral embodiments, T is selected from the group consisting of n-octyl,heptafluoroisopropoxypropyl, nonafluorohexyl, tridecafluorohexyl,trifluoromethyl, or combinations thereof. In several embodiments, thesurface is that of a diamond.

Some embodiments pertain to method of preparing the surface comprisingexposing the surface to a reagent selected from:heptafluoroisopropoxypropyltrichlorosilane,heptafluoroisopropoxypropyltrimethoxysilane,bis(nonafluorohexyldimethylsiloxy)methyl-silylethyldimethylchlorosilane,tridecafluoro-2-(tridecafluorohexyl)decyltrichlorosilane,heneicocyl-1,1,2,2-tetrahydrodecyltrichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)methyldichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyldichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane,n-octyltrichlorosilane, or combinations thereof. In several embodiments,the method comprises exposing the surface to plasma treatment prior toexposure to the reagent.

Some embodiments pertain to a diamond made by the methods disclosedabove and/or a diamond having a surface as disclosed above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a representation of a raw diamond surface having variousfunctional groups.

FIGS. 1B-1F are photographs and angular spectrum evaluation tool (ASET)images and SEM images of clean and soiled diamonds. FIGS. 1B and 1D showa photograph and an ASET image, respectively, of a clean diamond. FIGS.1C and 1E show a photograph and an ASET image, respectively, of a dirtydiamond. FIG. 1F shows a representative SEM image of a fouled diamondhaving dirt particles and grime accumulated (see arrows). The scale barsindicate 2 mm and 200 μm.

FIGS. 2A and 2B show schemes providing embodiments for functionalizing asubstrate surface and a diamond surface, respectively. As shown in FIGS.2A and 2B, respectively, the substrate and diamond surface can besubject to plasma treatment in Step A to provide a Precursor Surface onthe substrate or diamond. As shown in FIGS. 2A and 2B, respectively, inStep B, the substrate and diamond surface can be subject to annealingwith water to provide a Reactive Surface. As shown in FIGS. 2A and 2B,respectively, the surface of the substrate and diamond may be silanizedin Step C to provide a coated substrate and coated diamond surface. Thesubstituent R provides desired surface properties of the substrate anddiamond, respectively. Natural, lab grown, and other diamond crystalshave a mixture of chemical states. Treatment by hydrogen and oxygenplasma combined with a furnace treatment to convert surface hydrogen tooxygen-containing species renders the substrate receptive to coating.

FIG. 3 is a schematic showing an annealing apparatus and process. Asshown, nitrogen gas can be bubble through ultrapure water to generatenitrogen and water vapor. The nitrogen and water vapor a passed into afurnace (e.g., electric furnace) where an article comprising a precursorarticle having a Precursor Surface (e.g., a Precursor Diamond Surface)is located. The furnace heats the vapor and the precursor articlethereby depositing reactive oxygen species onto the substrate surface.

FIG. 4 shows a raw diamond in the left pane and a coated diamond in theright pane. To prepare the coated diamond, the raw diamond was modifiedto be hydrophilic by conversion of surface chemical sites to reactiveoxygen species. In the right pane, the diamond has been functionalizedwith a silane comprising a perfluoroalkyl tail. The reactive oxygenspecies are receptive to subsequent coating.

FIG. 5 provides another scheme showing a two-step process for preparinga diamond with a soil resistant silane surface. In several embodiments,R is an optionally substituted alkyl. In several embodiments, R is analkyl comprising a perfluorinated portion.

DETAILED DESCRIPTION

Some embodiments disclosed here pertain to molecular coatings forgemstones (e.g., diamonds), methods of coating gemstones, and methods ofusing gemstone coatings to resist dulling of gemstones. In severalembodiments, the gemstone is a diamond. In several embodiments, themolecular coating comprises a silane or siloxane molecule with asubstituent (e.g., a tail) having a desired property. In severalembodiments, the substituent alters the physical properties of thegemstone. For instance, in some embodiments, hydrophobic gem surfacescan be converted to hydrophilic surfaces using a hydrophilic hostmolecule. Conversely, in some embodiments, hydrophilic gem surfaces canbe converted to hydrophobic surfaces using a hydrophobic host molecule.Alternatively, a hydrophilic, hydrophobic, or amphiphilic surface can beconverted to an amphiphobic surface. In several embodiments, mixedsurfaces (hydrophilic, amphiphilic, or hydrophobic) can be achievedthrough the selection of varying substituents. The following descriptionprovides context and examples, but should not be interpreted to limitthe scope of the inventions covered by the claims that follow in thisspecification or in any other application that claims priority to thisspecification. No single component or collection of components isessential or indispensable.

Whenever a group is described as being “optionally substituted” thatgroup may be unsubstituted or substituted with one or more of theindicated substituents. Likewise, when a group is described as being“unsubstituted or substituted” (or “substituted or unsubstituted”) ifsubstituted, the substituent(s) may be selected from one or more theindicated substituents. If no substituents are indicated, it is meantthat the indicated “optionally substituted” or “substituted” group maybe substituted with one or more group(s) individually and independentlyselected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,heteroaryl, heterocyclyl, aryl(alkyl), cycloalkyl(alkyl),heteroaryl(alkyl), heterocyclyl(alkyl), alkoxy, halogen, haloalkyl,haloalkoxy, an amino, a mono substituted amine group, a di substitutedamine group, a mono substituted amine(alkyl), a di substitutedamine(alkyl), a diamino-group, a polyamino, a diether-group, and apolyether-. An optionally substituted group may be perhalogenated (e.g.,perfluoro). For instance, optionally substituted methyl may include—CF₃. Additionally, a substituent, when presented on an optionallysubstituted compound may be halogenated (e.g., fluorinated) and/orperhalogenated (e.g., perfluoro). For instance, optionally substitutedethyl may include an ethyl with a perfluorinated cycloalkyl as itsoptional substituent. For further illustration, optionally substitutedethyl may include perfluorinated ethyl with a perfluorinated cycloalkylas its optional substituent.

As used herein, “C_(a) to C_(b)” in which “a” and “b” are integers referto the number of carbon atoms in a group. The indicated group cancontain from “a” to “b”, inclusive, carbon atoms. Thus, for example, a“C₁ to C₄ alkyl” group refers to all alkyl groups having from 1 to 4carbons, that is, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, (CH₃)₂CH—, CH₃CH₂CH₂CH₂—,CH₃CH₂CH(CH₃)— and (CH₃)₃C—. If no “a” and “b” are designated, thebroadest range described in these definitions is to be assumed.Similarly, C₁₋₄ alkyl has the same meaning as C₁ to C₄ alkyl.

If two “R” groups are described as being “taken together” the R groupsand the atoms they are attached to can form a cycloalkyl, cycloalkenyl,aryl, heteroaryl or heterocycle. For example, without limitation, ifR^(a) and R^(b) of an NR^(a)R^(b) group are indicated to be “takentogether,” it means that they are covalently bonded to one another toform a ring:

As used herein, the term “alkyl” refers to a fully saturated aliphatichydrocarbon group. The alkyl moiety may be branched or straight chain.Examples of branched alkyl groups include, but are not limited to,iso-propyl, sec-butyl, t-butyl and the like. Examples of straight chainalkyl groups include, but are not limited to, methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl and the like. The alkyl group mayhave 1 to 30 carbon atoms (whenever it appears herein, a numerical rangesuch as “1 to 30” refers to each integer in the given range; e.g., “1 to30 carbon atoms” means that the alkyl group may consist of 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, or 30 carbon atoms, although the presentdefinition also covers the occurrence of the term “alkyl” where nonumerical range is designated). The “alkyl” group may also be a mediumsize alkyl having 1 to 12 carbon atoms. The “alkyl” group could also bea lower alkyl having 1 to 6 carbon atoms. By way of example only, “C₁-C₅alkyl” indicates that there are one to five carbon atoms in the alkylchain, i.e., the alkyl chain is selected from methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, pentyl (branched andstraight-chained), etc. Typical alkyl groups include, but are in no waylimited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiarybutyl, pentyl and hexyl.

Any “alkyl” group disclosed herein may be substituted or unsubstituted.For instance, an alkyl disclosed herein may be substituted whether ornot indicated as “substituted” or “optionally substituted”. Optionalsubstitutions of alkyl groups may include those described elsewhereherein. For instance, where optionally substituted, an alkyl may besubstituted with halogen atoms. To illustrate, an optionally substitutedalkyl may be halogenated (having one or more —H atoms replaced by—X^(H), where X^(H) is halogen). As an additional illustration, anoptionally substituted alkyl may be perhalogenated (e.g.,perfluorinated, where each —H atom is replaced with a —F) or partiallyhalogenated.

As used herein, the term “alkylene” refers to a bivalent fully saturatedstraight chain aliphatic hydrocarbon group. Examples of alkylene groupsinclude, but are not limited to, methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene and octylene. An alkylene groupmay be represented by

, followed by the number of carbon atoms, followed by a “*”. Forexample,

to represent ethylene. The alkylene group may have 1 to 30 carbon atoms(whenever it appears herein, a numerical range such as “1 to 30” refersto each integer in the given range; e.g., “1 to 30 carbon atoms” meansthat the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3carbon atoms, etc., up to and including 30 carbon atoms, although thepresent definition also covers the occurrence of the term “alkylene”where no numerical range is designated). The alkylene group may also bea medium size alkyl having 1 to 12 carbon atoms. The alkylene groupcould also be a lower alkyl having 1 to 6 carbon atoms. An alkylenegroup may be substituted or unsubstituted. For example, a lower alkylenegroup can be substituted by replacing one or more hydrogen of the loweralkylene group and/or by substituting both hydrogens on the same carbonwith a C₃₋₆ monocyclic cycloalkyl group

As disclosed elsewhere herein, where requiring to attachment points, analkyl may be alkylenyl.

The term “alkenyl” used herein refers to a monovalent straight orbranched chain radical of from two to twenty carbon atoms containing acarbon double bond(s) including, but not limited to, 1-propenyl,2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl and the like. Analkenyl group may be unsubstituted or substituted.

The term “alkynyl” used herein refers to a monovalent straight orbranched chain radical of from two to twenty carbon atoms containing acarbon triple bond(s) including, but not limited to, 1-propynyl,1-butynyl, 2-butynyl and the like. An alkynyl group may be unsubstitutedor substituted.

As used herein, “cycloalkyl” refers to a completely saturated (no doubleor triple bonds) mono- or multi-cyclic (such as bicyclic) hydrocarbonring system. When composed of two or more rings, the rings may be joinedtogether in a fused, bridged or spiro fashion. As used herein, the term“fused” refers to two rings which have two atoms and one bond in common.As used herein, the term “bridged cycloalkyl” refers to compoundswherein the cycloalkyl contains a linkage of one or more atomsconnecting non-adjacent atoms. As used herein, the term “spiro” refersto two rings which have one atom in common and the two rings are notlinked by a bridge. Cycloalkyl groups can contain 3 to 30 atoms in thering(s), 3 to 20 atoms in the ring(s), 3 to 10 atoms in the ring(s), 3to 8 atoms in the ring(s) or 3 to 6 atoms in the ring(s). A cycloalkylgroup may be unsubstituted or substituted. Examples of mono-cycloalkylgroups include, but are in no way limited to, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of fusedcycloalkyl groups are decahydronaphthalenyl, dodecahydro-1H-phenalenyland tetradecahydroanthracenyl; examples of bridged cycloalkyl groups arebicyclo[1.1.1]pentyl, adamantanyl and norbornanyl; and examples of spirocycloalkyl groups include spiro[3.3]heptane and spiro[4.5]decane.

As used herein, “cycloalkenyl” refers to a mono- or multi-cyclic (suchas bicyclic) hydrocarbon ring system that contains one or more doublebonds in at least one ring; although, if there is more than one, thedouble bonds cannot form a fully delocalized pi-electron systemthroughout all the rings (otherwise the group would be “aryl,” asdefined herein). Cycloalkenyl groups can contain 3 to 10 atoms in thering(s), 3 to 8 atoms in the ring(s) or 3 to 6 atoms in the ring(s).When composed of two or more rings, the rings may be connected togetherin a fused, bridged or spiro fashion. A cycloalkenyl group may beunsubstituted or substituted.

As used herein, “aryl” refers to a carbocyclic (all carbon) monocyclicor multicyclic (such as bicyclic) aromatic ring system (including fusedring systems where two carbocyclic rings share a chemical bond) that hasa fully delocalized pi-electron system throughout all the rings. Thenumber of carbon atoms in an aryl group can vary. For example, the arylgroup can be a C₆-C₁₄ aryl group, a C₆-C₁₀ aryl group or a C₆ arylgroup. Examples of aryl groups include, but are not limited to, benzene,naphthalene and azulene. An aryl group may be substituted orunsubstituted. As used herein, “heteroaryl” refers to a monocyclic ormulticyclic (such as bicyclic) aromatic ring system (a ring system withfully delocalized pi-electron system) that contain(s) one or moreheteroatoms (for example, 1, 2 or 3 heteroatoms), that is, an elementother than carbon, including but not limited to, nitrogen, oxygen andsulfur. The number of atoms in the ring(s) of a heteroaryl group canvary. For example, the heteroaryl group can contain 4 to 14 atoms in thering(s), 5 to 10 atoms in the ring(s) or 5 to 6 atoms in the ring(s),such as nine carbon atoms and one heteroatom; eight carbon atoms and twoheteroatoms; seven carbon atoms and three heteroatoms; eight carbonatoms and one heteroatom; seven carbon atoms and two heteroatoms; sixcarbon atoms and three heteroatoms; five carbon atoms and fourheteroatoms; five carbon atoms and one heteroatom; four carbon atoms andtwo heteroatoms; three carbon atoms and three heteroatoms; four carbonatoms and one heteroatom; three carbon atoms and two heteroatoms; or twocarbon atoms and three heteroatoms. Furthermore, the term “heteroaryl”includes fused ring systems where two rings, such as at least one arylring and at least one heteroaryl ring or at least two heteroaryl rings,share at least one chemical bond. Examples of heteroaryl rings include,but are not limited to, furan, furazan, thiophene, benzothiophene,phthalazine, pyrrole, oxazole, benzoxazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, thiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole,benzothiazole, imidazole, benzimidazole, indole, indazole, pyrazole,benzopyrazole, isoxazole, benzoisoxazole, isothiazole, triazole,benzotriazole, thiadiazole, tetrazole, pyridine, pyridazine, pyrimidine,pyrazine, purine, pteridine, quinoline, isoquinoline, quinazoline,quinoxaline, cinnoline and triazine. A heteroaryl group may besubstituted or unsubstituted.

As used herein, “heterocyclyl” or “heteroalicyclyl” refers to three-,four-, five-, six-, seven-, eight-, nine-, ten-, up to 18-memberedmonocyclic, bicyclic and tricyclic ring system wherein carbon atomstogether with from 1 to 5 heteroatoms constitute said ring system. Aheterocycle may optionally contain one or more unsaturated bondssituated in such a way, however, that a fully delocalized pi-electronsystem does not occur throughout all the rings. The heteroatom(s) is anelement other than carbon including, but not limited to, oxygen, sulfurand nitrogen. A heterocycle may further contain one or more carbonyl orthiocarbonyl functionalities, so as to make the definition includeoxo-systems and thio-systems such as lactams, lactones, cyclic imides,cyclic thioimides and cyclic carbamates. When composed of two or morerings, the rings may be joined together in a fused, bridged or spirofashion. As used herein, the term “fused” refers to two rings which havetwo atoms and one bond in common. As used herein, the term “bridgedheterocyclyl” or “bridged heteroalicyclyl” refers to compounds whereinthe heterocyclyl or heteroalicyclyl contains a linkage of one or moreatoms connecting non-adjacent atoms. As used herein, the term “spiro”refers to two rings which have one atom in common and the two rings arenot linked by a bridge. Heterocyclyl and heteroalicyclyl groups cancontain 3 to 30 atoms in the ring(s), 3 to 20 atoms in the ring(s), 3 to10 atoms in the ring(s), 3 to 8 atoms in the ring(s) or 3 to 6 atoms inthe ring(s). For example, five carbon atoms and one heteroatom; fourcarbon atoms and two heteroatoms; three carbon atoms and threeheteroatoms; four carbon atoms and one heteroatom; three carbon atomsand two heteroatoms; two carbon atoms and three heteroatoms; one carbonatom and four heteroatoms; three carbon atoms and one heteroatom; or twocarbon atoms and one heteroatom. Additionally, any nitrogens in aheteroalicyclic may be quaternized. Heterocyclyl or heteroalicyclicgroups may be unsubstituted or substituted. Examples of such“heterocyclyl” or “heteroalicyclyl” groups include but are not limitedto, 1,3-dioxin, 1,3-dioxane, 1,4-dioxane, 1,2-dioxolane, 1,3-dioxolane,1,4-dioxolane, 1,3-oxathiane, 1,4-oxathiin, 1,3-oxathiolane,1,3-dithiole, 1,3-dithiolane, 1,4-oxathiane, tetrahydro-1,4-thiazine,2H-1,2-oxazine, maleimide, succinimide, barbituric acid, thiobarbituricacid, dioxopiperazine, hydantoin, dihydrouracil, trioxane,hexahydro-1,3,5-triazine, imidazoline, imidazolidine, isoxazoline,isoxazolidine, oxazoline, oxazolidine, oxazolidinone, thiazoline,thiazolidine, morpholine, oxirane, piperidine N-Oxide, piperidine,piperazine, pyrrolidine, azepane, pyrrolidone, pyrrolidione,4-piperidone, pyrazoline, pyrazolidine, 2-oxopyrrolidine,tetrahydropyran, 4H-pyran, tetrahydrothiopyran, thiamorpholine,thiamorpholine sulfoxide, thiamorpholine sulfone and their benzo-fusedanalogs (e.g., benzimidazolidinone, tetrahydroquinoline and/or3,4-methylenedioxyphenyl). Examples of spiro heterocyclyl groups include2-azaspiro[3.3]heptane, 2-oxaspiro[3.3]heptane,2-oxa-6-azaspiro[3.3]heptane, 2,6-diazaspiro[3.3]heptane,2-oxaspiro[3.4]octane and 2-azaspiro[3.4]octane.

As used herein, “aralkyl” and “aryl(alkyl)” refer to an aryl groupconnected, as a substituent, via a lower alkylene group. The loweralkylene and aryl group of an aralkyl may be substituted orunsubstituted. Examples include but are not limited to benzyl,2-phenylalkyl, 3-phenylalkyl and naphthylalkyl.

As used herein, “cycloalkyl(alkyl)” refer to an cycloalkyl groupconnected, as a substituent, via a lower alkylene group. The loweralkylene and cycloalkyl group of a cycloalkyl(alkyl) may be substitutedor unsubstituted.

As used herein, “heteroaralkyl” and “heteroaryl(alkyl)” refer to aheteroaryl group connected, as a substituent, via a lower alkylenegroup. The lower alkylene and heteroaryl group of heteroaralkyl may besubstituted or unsubstituted. Examples include but are not limited to2-thienylalkyl, 3-thienylalkyl, furylalkyl, thienylalkyl, pyrrolylalkyl,pyridylalkyl, isoxazolylalkyl and imidazolylalkyl and their benzo-fusedanalogs.

A “heteroalicyclyl(alkyl)” and “heterocyclyl(alkyl)” refer to aheterocyclic or a heteroalicyclic group connected, as a substituent, viaa lower alkylene group. The lower alkylene and heterocyclyl of a(heteroalicyclyl)alkyl may be substituted or unsubstituted. Examplesinclude but are not limited tetrahydro-2H-pyran-4-yl(methyl),piperidin-4-yl(ethyl), piperidin-4-yl(propyl),tetrahydro-2H-thiopyran-4-yl(methyl) and 1,3-thiazinan-4-yl(methyl).

As used herein, the term “hydroxy” refers to a —OH group.

As used herein, “alkoxy” refers to the Formula —OR wherein R is analkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkenyl, aryl,heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl),heteroaryl(alkyl) or heterocyclyl(alkyl) is defined herein. Anon-limiting list of alkoxys are methoxy, ethoxy, n-propoxy,1-methylethoxy (isopropoxy), n-butoxy, iso-butoxy, sec-butoxy,tert-butoxy, phenoxy and benzoxy. An alkoxy may be substituted orunsubstituted.

The term “halogen atom” or “halogen” (e.g., —X^(H)) as used herein,means any one of the radio-stable atoms of column 7 of the PeriodicTable of the Elements, such as, fluorine (—F), chlorine (—Cl), bromine(—Br), and iodine (—I).

As used herein, “haloalkyl” refers to an alkyl group in which one ormore of the hydrogen atoms (or all) are replaced by a halogen (e.g.,mono-haloalkyl, di-haloalkyl, tri-haloalkyl, polyhaloalkyl, andperhaloalkyl). The haloalkyl moiety may be branched or straight chain.Such groups include but are not limited to, chloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, 1-chloro-2-fluoromethyl,2-fluoroisobutyl and pentafluoroethyl. Examples of haloalkyl groupsinclude, but are not limited to, —CF₃, —CHF₂, —CH₂F, —CH₂CF₃, —CH₂CHF₂,—CH₂CH₂F, —CH₂CH₂Cl, —CH₂CF₂CF₃, —CF₂CF₂CF₃; —CF₂—CF₂—CF₂—CF₃; and othergroups that in light of the ordinary skill in the art and the teachingsprovided herein, would be considered equivalent to any one of theforegoing examples (including fluoroalkyls). The haloalkyl may be amedium sized or lower haloalkyl. A haloalkyl may be represented by—(C(X^(H))₂)_(m)—X^(H), where “m” is any integer between 1 and 20. Ahaloalkyl may be substituted or unsubstituted.

As used herein, “fluoroalkyl” refers to an haloalkyl group (or alkylgroup) in which one or more of the hydrogen atoms are replaced by afluorine (e.g., mono-fluoroalkyl, di-fluoroalkyl, tri-fluoroalkyl,polyfluoroalkyl, and perfluoroalkyl). Such groups include but are notlimited to, fluoromethyl, difluoromethyl, trifluoromethyl,2-fluoroisobutyl and pentafluoroethyl. Examples of haloalkyl groupsinclude, but are not limited to, —CF₃, —CHF₂, —CH₂F, —CH₂CF₃, —CH₂CHF₂,—CH₂CH₂F, —CH₂CH₂Cl, —CH₂CF₂CF₃, —CF₂CF₂CF₃; —CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₃; —CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃; —CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃;—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃; and other groupsthat in light of the ordinary skill in the art and the teachingsprovided herein, would be considered equivalent to any one of theforegoing examples. A fluoroalkyl may be a medium sized or lowerfluoroalkyl. A fluoroalkyl may be represented by —(C(X^(H))₂)_(m)—X^(H),where X^(H) is —F and “m” is any integer between 1 and 20. A fluoroalkylmay be a C₄ to C₁₀ fluoroalkyl, a C₆ to C₁₂ fluoroalkyl, a C₈ to C₁₄fluoroalkyl, a C₁ to C₁₅ fluoroalkyl, a C₆ to C₂₀ fluoroalkyl, or thelike.

As used herein, “haloalkoxy” refers to an alkoxy group in which one ormore of the hydrogen atoms are replaced by a halogen (e.g.,mono-haloalkoxy, di-haloalkoxy and tri-haloalkoxy). Such groups includebut are not limited to, chloromethoxy, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 1-chloro-2-fluoromethoxy and 2-fluoroisobutoxy. Thehaloalkoxy may be a medium sized or lower haloalkoxy. A haloalkoxy maybe represented by —O—(C(X^(H))₂)_(n)—X^(H), where “n” is any integerbetween 1 and 20. A haloalkoxy may be substituted or unsubstituted.

The terms “amino” and “unsubstituted amino” as used herein refer to a—NH₂ group.

A “mono-substituted amine” group refers to a “—NHR_(A)” group in whichR_(A) can be an alkyl, an alkenyl, an alkynyl, a cycloalkyl, acycloalkenyl, aryl, heteroaryl, heterocyclyl, cycloalkyl(alkyl),aryl(alkyl), heteroaryl(alkyl) or heterocyclyl(alkyl), as definedherein. The R_(A) may be substituted or unsubstituted. Amono-substituted amine group can include, for example, a mono-alkylaminegroup, a mono-C₁-C₆ alkylamine group, a mono-arylamine group, amono-C₆-C₁₀ arylamine group and the like. Examples of mono-substitutedamine groups include, but are not limited to, —NH(methyl), —NH(phenyl)and the like.

A “di-substituted amine” group refers to a “—NRAR_(B)” group in whichR_(A) and R_(B) can be independently an alkyl, an alkenyl, an alkynyl, acycloalkyl, a cycloalkenyl, aryl, heteroaryl, heterocyclyl,cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) orheterocyclyl(alkyl), as defined herein. R_(A) and R_(B) canindependently be substituted or unsubstituted. A di-substituted aminegroup can include, for example, a di-alkylamine group, a di-C₁-C₆alkylamine group, a di-arylamine group, a di-C₆-C₁₀ arylamine group andthe like. Examples of di-substituted amine groups include, but are notlimited to, —N(methyl)₂, —N(phenyl)(methyl), —N(ethyl)(methyl) and thelike.

As used herein, “mono-substituted amine(alkyl)” group refers to amono-substituted amine as provided herein connected, as a substituent,via a lower alkylene group. A mono-substituted amine(alkyl) may besubstituted or unsubstituted. A mono-substituted amine(alkyl) group caninclude, for example, a mono-alkylamine(alkyl) group, a mono-C₁-C₆alkylamine(C₁-C₆ alkyl) group, a mono-arylamine(alkyl group), amono-C₆-C₁₀ arylamine(C₁-C₆ alkyl) group and the like. Examples ofmono-substituted amine(alkyl) groups include, but are not limited to,—CH₂NH(methyl), —CH₂NH(phenyl), —CH₂CH₂NH(methyl), —CH₂CH₂NH(phenyl) andthe like.

As used herein, “di-substituted amine(alkyl)” group refers to adi-substituted amine as provided herein connected, as a substituent, viaa lower alkylene group. A di-substituted amine(alkyl) may be substitutedor unsubstituted. A di-substituted amine(alkyl) group can include, forexample, a dialkylamine(alkyl) group, a di-C₁-C₆ alkylamine(C₁-C₆ alkyl)group, a di-arylamine(alkyl) group, a di-C₆-C₁₀ arylamine(C₁-C₆ alkyl)group and the like. Examples of di-substituted amine(alkyl)groupsinclude, but are not limited to, —CH₂N(methyl)₂, —CH₂N(phenyl)(methyl),—CH₂N(ethyl)(methyl), —CH₂CH₂N(methyl)₂, —CH₂CH₂N(phenyl)(methyl),—NCH₂CH₂(ethyl)(methyl) and the like.

As used herein, the term “diamino-” denotes an a“—N(R_(A))R_(B)—N(R_(C))(R_(D))” group in which R_(A), R_(C), and R_(D)can be independently a hydrogen, an alkyl, an alkenyl, an alkynyl, acycloalkyl, a cycloalkenyl, aryl, heteroaryl, heterocyclyl,cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) orheterocyclyl(alkyl), as defined herein, and wherein R_(B) connects thetwo “N” groups and can be (independently of R_(A), R_(C), and R_(D)) asubstituted or unsubstituted alkylene group. R_(A), R_(B), R_(C), andR_(D) can independently further be substituted or unsubstituted.

As used herein, the term “polyamino” denotes a“—(N(R_(A))R_(B)—)_(n)—N(R_(C))(R_(D))”. For illustration, the termpolyamino can comprise—N(R_(A))alkyl-N(R_(A))alkyl-N(R_(A))alkyl-N(R_(A))alkyl-H. In severalembodiments, the alkyl of the polyamino is as disclosed elsewhereherein. While this example has only 4 repeat units, the term “polyamino”may consist of 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 repeat units. R_(A),R_(C), and R_(D) can be independently a hydrogen, an alkyl, an alkenyl,an alkynyl, a cycloalkyl, a cycloalkenyl, aryl, heteroaryl,heterocyclyl, cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) orheterocyclyl(alkyl), as defined herein, and wherein R_(B) connects thetwo “N” groups and can be (independently of R_(A), R_(C), and R_(D)) asubstituted or unsubstituted alkylene group. R_(A), R_(C), and R_(D) canindependently further be substituted or unsubstituted. As noted here,the polyamino comprises amine groups with intervening alkyl groups(where alkyl is as defined elsewhere herein).

As used herein, the term “diether-” denotes an a “—OR_(B)O—R_(A)” groupin which R_(A) can be a hydrogen, an alkyl, an alkenyl, an alkynyl, acycloalkyl, a cycloalkenyl, aryl, heteroaryl, heterocyclyl,cycloalkyl(alkyl), aryl(alkyl), heteroaryl(alkyl) orheterocyclyl(alkyl), as defined herein, and wherein R_(B) connects thetwo “O” groups and can be a substituted or unsubstituted alkylene group.R_(A) can independently further be substituted or unsubstituted.

As used herein, the term “polyether” denotes a repeating—(OR_(B)—)_(n)OR_(A) group. For illustration, the term polyether cancomprise —Oalkyl-Oalkyl-Oalkyl-Oalkyl-OR_(A). In several embodiments,the alkyl of the polyether is as disclosed elsewhere herein. While thisexample has only 4 repeat units, the term “polyether” may consist of 1,2, 3, 4, 5, 6, 7, 8, 9, or 10 repeat units. R_(A) can be a hydrogen, analkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkenyl, aryl,heteroaryl, heterocyclyl, cycloalkyl(alkyl), aryl(alkyl),heteroaryl(alkyl) or heterocyclyl(alkyl), as defined herein. R_(B) canbe a substituted or unsubstituted alkylene group. R_(A) canindependently further be substituted or unsubstituted. As noted here,the polyether comprises ether groups with intervening alkyl groups(where alkyl is as defined elsewhere herein and can be optionallysubstituted).

Where the number of substituents is not specified (e.g. haloalkyl),there may be one or more substituents present (e.g., 1, 2, 3, 4, 5, 6,7, or more). For example, “haloalkyl” may include one or more of thesame or different halogens. As another example, “C₁-C₃ alkoxyphenyl” mayinclude one or more of the same or different alkoxy groups containingone, two or three atoms.

Wherever a substituent is depicted as a di-radical (i.e., has two pointsof attachment to the rest of the molecule), it is to be understood thatthe substituent can be attached in any directional configuration unlessotherwise indicated. Thus, for example, a substituent depicted as -AE-or

includes the substituent being oriented such that the “A” is attached atthe leftmost attachment point of the molecule as well as the case inwhich “A” is attached at the rightmost attachment point of the molecule.

As noted in the definition for alkylene, it also is to be understoodthat certain radical naming conventions can include either amono-radical or a di-radical, depending on the context. For example,where a substituent requires two points of attachment to the rest of themolecule, it is understood that the substituent is a di-radical. Forexample, a substituent identified as alkyl that requires two points ofattachment includes di-radicals such as —CH₂—, —CH₂CH₂—,—CH₂CH(CH₃)CH₂—, and the like. Other examples a substituent may requiretwo points of attachment include alkoxy, aryl, heteroaryl, carbocyclyl,heterocyclyl, etc.

As used herein, a radical indicates species with a single, unpairedelectron such that the species containing the radical can be covalentlybonded to another species. Hence, in this context, a radical is notnecessarily a free radical. Rather, a radical indicates a specificportion of a larger molecule. The term “radical” can be usedinterchangeably with the term “group.”

When referring to a quantity or amount, the terms “or ranges includingand/or spanning the aforementioned values” (and variations thereof) ismeant to include any range that includes or spans the aforementionedvalues. For example, when the contact angle is expressed as “80°, 90°,100°, 110°, or ranges including and/or spanning the aforementionedvalues,” this includes the particular contact angle provided (e.g., acontact angle equal to any one of 80°, 90°, 100°, or 110°) or contactangle ranges spanning the aforementioned values (e.g., from 80° to 110°,80° to 100°, 80° to 90°, 90° to 110°, 90° to 100°, and 100° to 20%).

As used herein, a “natural diamond” refers to diamond that has not beenchemically modified. A natural diamond may include a diamond that hasbeen cut and shaped.

As used herein, a “raw diamond” is a natural diamond prior to plasmatreatment and/or silanization.

Terms and phrases used in this application, and variations thereof,especially in the appended claims, unless otherwise expressly stated,should be construed as open ended as opposed to limiting. As examples ofthe foregoing, the term “including” should be read to mean “including,without limitation,” “including but not limited to,” or the like; theterm “comprising” as used herein is synonymous with “including,”“containing,” or “characterized by,” and is inclusive or open-ended anddoes not exclude additional, unrecited elements or method steps; theterm “having” should be interpreted as “having at least;” the term“includes” should be interpreted as “includes but is not limited to;”the term “example” is used to provide exemplary instances of the item indiscussion, not an exhaustive or limiting list thereof; and use of termslike “preferably,” “preferred,” “desired,” or “desirable,” and words ofsimilar meaning should not be understood as implying that certainfeatures are critical, essential, or even important to the structure orfunction of the invention, but instead as merely intended to highlightalternative or additional features that may or may not be utilized in aparticular embodiment of the invention. In addition, the term“comprising” is to be interpreted synonymously with the phrases “havingat least” or “including at least”. When used in the context of aprocess, the term “comprising” means that the process includes at leastthe recited steps, but may include additional steps. When used in thecontext of a compound, composition or device, the term “comprising”means that the compound, composition or device includes at least therecited features or components, but may also include additional featuresor components. Likewise, a group of items linked with the conjunction‘and’ should not be read as requiring that each and every one of thoseitems be present in the grouping, but rather should be read as ‘and/or’unless expressly stated otherwise. Similarly, a group of items linkedwith the conjunction ‘or’ should not be read as requiring mutualexclusivity among that group, but rather should be read as ‘and/or’unless expressly stated otherwise.

Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity. The indefinite article “a” or “an” does not exclude aplurality. A single processor or other unit may fulfill the functions ofseveral items recited in the claims. The mere fact that certain measuresare recited in mutually different dependent claims does not indicatethat a combination of these measures cannot be used to advantage. Anyreference signs in the claims should not be construed as limiting thescope.

The section headings used herein are for organizational purposes onlyand are not to be construed as limiting the subject matter described.Features disclosed under one heading (such as an antifouling surface)can be used in combination with features disclosed under a differentheading (a method of using an antifouling surface). Unless definedotherwise, all technical and scientific terms used herein have the samemeaning as is commonly understood by one of ordinary skill in the art.It should be noted that the use of particular terminology whendescribing certain features or aspects of the disclosure should not betaken to imply that the terminology is being re-defined herein to berestricted to include any specific characteristics of the features oraspects of the disclosure with which that terminology is associated.

INTRODUCTION

Diamond is a carbon crystal where carbon atoms are arranged in a regularlattice. In a diamond, the carbon atoms are arranged tetrahedrally. Eachcarbon atom is attached to four other carbon atoms 1.544×10⁻¹⁰ meter(1.544 angstroms (Å)) away. Three adjacent carbons make create a bondangle of 109.5°. The diamond lattice is a strong, rigidthree-dimensional structure that results in a large network of atoms.While internal portions of a diamond are substantially pure carbon, atthe surface, a natural cut diamond that comprises C—H bonds, epoxidegroups, carbonyl groups, carboxylic acid groups, and hydroxyl groups. Arepresentation of a raw diamond surface is shown in FIG. 1A. Less than10% of the surface carbon atoms are linked to an acidic and/or carbonylgroup. A small percentage of the surface area of a diamond surfaceincludes hydroxyl groups. As such, the surface of a diamond ishydrophobic.

Given the hydrophobicity of natural diamond, as jewelry diamonds areworn or stored, the hydrophobic carbon lattice of the diamond begins toattract grease and grime. Over time, grease and grime builds up anddulls the diamond's brilliance and fire. This build-up is shown in FIGS.1B to 1F for diamonds. FIGS. 1B and 1D, respectively, show a photographand an ASET image of a clean diamond. FIGS. 1C and 1E, respectively,show a photograph and an ASET images of a dirty diamond. As can benoted, FIGS. 1C and 1E have less shine and brilliance than the cleandiamond of FIGS. 1B and 1D. FIG. 1F shows a representative SEM image ofa fouled diamond that shows dirt and grime accumulated (see arrows). Thescale bars indicate 2 mm and 200 μm. This dirt and grime build-up and/orfouling can significantly reduce the user's enjoyment of their jewelry.

As disclosed elsewhere herein, this build-up happens at least in partdue to the surface of a diamond being intrinsically hydrophobic. As ahydrophobic surface, it attracts hydrophobic residues, such as, smudges(from fingerprints), oil, grease, and grime. Diamonds naturally attractgrease (lipophilic), but repel water (hydrophobic). This is a reason whythe fire and brilliance that attracts consumers to diamond jewelry isquickly lost after they leave the showroom. Upon the mere touch of ahuman finger, oils and lotions can be transferred to the clean crystalsurface. Once the crystal is fouled by these chemicals, dirt, protein,or other debris can more easily bind nonspecifically to the crystal andthereby diminish its sparkling appeal. This buildup is evident by visualinspection as well as ASET analysis, and can be observed in SEM as shownin FIGS. 1B-1F.

There are two conventional remedies to clean the grease and grime buildup from the diamonds. The first is professional and/or commercial. Ajeweler can clean soiled stones using an ultrasonic cleaner and/or acleaning solution containing non-polar solvents. After cleaning, thebrilliance and shine of the diamonds is restored (e.g., they areshowroom-new). However, grease and grime will begin to accumulate assoon as the user leaves the showroom, because the diamond ishydrophobic. The second remedy consists of home cleaning products. Manyhome cleaners exist and work with varying degrees of success. Most willnot clean the diamonds enough to restore the showroom-new brilliance ofthe stones. Furthermore, current solutions are merely restorative,meaning that any improvement in brilliance begins to fade immediately.

Maintenance of the pristine optical properties of jewelry for everydayuse is a major challenge. Cleaning requires repetitive, tedious laborwith chemical solutions and special tools. Finished jewelry items(comprising jewelry gemstones) are often physically complex with manydifferently sized stones and confined spaces between the stones andsettings. Continuous maintenance can be done at home by chemical soaking(>2×/week), combined with an abrasive, mechanical action, such as a softtoothbrush, to remove remaining dirt, especially hard-to-reach placeslike the back of the diamond, which tends to collect the mostcontamination. Alternatively, ultrasonic cleaners are usedprofessionally and are marketed to home users. While such cleaners canmore effectively remove accumulated dirt and grime on diamonds, they aretoo physically disruptive and can dislodge stones from their settings.Repeated ultrasonic cleaning of mounted stones can chip the girdles ofdiamonds that are set next to each other, resulting in irreversibledamage to the end product. Many end consumers lose interest inmaintenance and tolerate chronically soiled jewelry simply because thereare not practical viable alternatives. Both of the described currentcleaning methods are either passive or post-treatment, they remove theoffending material after it is present so that neither prevents theimmediate recontamination of the piece.

Several embodiments disclosed herein solve these or other problems byproviding soil-resistant coatings and methods of making and using suchsoil-resistant coatings. In several embodiments, a soil-resistantcoating prevents, delays, lowers the incidences of, and/or decreases theamount of oil, grime, or other material that adheres to a substrate(when comparing the coated substrate to an uncoated substrate). Inseveral embodiments, the coating comprises, consists of, or consistsessentially of a monolayer. In several embodiments, the monolayer isformed directly on a substrate (e.g., a diamond surface). In this way,an intermediate reaction layer (e.g., a layer that provides a reactive“handle” for a monolayer precursor molecule to bond with) is not neededand/or is completely absent. An intermediate layer may be a siloxanelayer over a substrate (e.g., a layer of SiO₂ covering the substrate).In several embodiments, the coated substrate lacks an intermediate layerbetween the monolayer and the substrate. For example, in severalembodiments, a monolayer precursor molecule is reacted directly andcovalently with a reactive group of the substrate. As such, a reactivegroup of the monolayer precursor molecule bonds (e.g., silanizing group)to a reactive group of the substrate forming a portion of the monolayer.

Advantageously, it has been found that pretreating the substrate in aspecified manner improves the quality of the substrate coating (primingit for reaction with a silanizing agent). In several embodiments, priorto monolayer formation on the substrate, the substrate is pretreatedand/or primed to receive and/or bond with the monolayer precursormolecule. In several embodiments, pretreatment has been found to allowdenser and/or more regular packing of the monolayer on the substrate.This denser packing improves soil resisting properties. In severalembodiments, pretreatment of the substrate improves the soil-resistantcoating's performance and durability (e.g., with regard to the longevityof soil-resistance and/or the ability to resist soiling in the firstplace).

In several embodiments, the pretreatment step includes a step of plasmatreating the substrate. Plasma is a mixture of neutral atoms, atomicions, electrons, molecular ions, and molecules present in excited andground states. Plasma may be generated by subjecting a gas to electriccurrent. In several embodiments, the pretreatment step is performedusing oxygen plasma or hydrogen plasma (or both). Oxygen plasma refersto any plasma process where oxygen is used in a plasma chamber togenerate plasma. Hydrogen plasma refers to any plasma process wherehydrogen is used in a plasma chamber to generate plasma. It has beenfound that oxygen and/or hydrogen treatment provides a plasma cleansedreactive substrate that is capable of accepting a more densely packedmonolayer (e.g., having more monolayer molecular units per unit area)and/or a more regular monolayer (e.g., having more regularity ofsoil-resistance per unit area). In several embodiments, the oxygenand/or hydrogen gas may be mixed with argon gas to provide the plasma.In several embodiments, argon is not required and/or is not used. Inseveral embodiments, the plasma gas used for pretreatment comprises,consists of, or consists essentially of oxygen. In several embodiments,the plasma gas used for pretreatment comprises, consists of, or consistsessentially of hydrogen. In several embodiments, the plasma gas used forpretreatment comprises, consists of, or consists essentially of oxygenand argon. In several embodiments, the plasma gas used for pretreatmentcomprises, consists of, or consists essentially of hydrogen and argon.

In several embodiments, the plasma treatment includes a single step(e.g., treatment with oxygen plasma or hydrogen plasma). In otherembodiments, the plasma treatment includes a multi-step plasma exposureregimen. For example, the regimen may include first a treatment withoxygen plasma, followed by treatment with hydrogen plasma (as a secondtreatment step). Alternatively, the regimen may include first atreatment with hydrogen plasma, followed by treatment with oxygen plasma(as a second treatment step). In several embodiments, as disclosedelsewhere herein, plasma treatment using oxygen plasma followed byhydrogen plasma (in two different steps), allows especially densepacking of reactive oxygen species after annealing.

In several embodiments, pretreatment of a substrate (e.g., the step ofpreparing the substrate surface for reaction to the monolayer precursormolecule) involves an additional step after plasma treatment. Forexample, the plasma treatment of the substrate may provide a precursorsubstrate. In several embodiments, the plasma treated substrate (e.g.,the precursor substrate) is annealed. In several embodiments, theannealing process converts additional surface functional groups on thesubstrate to reactive groups. In several embodiments, the plasma treatedsubstrate is annealed with water. In several embodiments, annealing withwater increases the relative ratio of hydroxyl groups and/or carboxylicacid groups on the substrate. In several embodiments, an annealing stepis beneficial to achieve desired levels of anti-soiling for a substrate(e.g., a diamond). In some embodiments, the annealing step may beomitted.

It has now been found that the high symmetry crystal planes of diamond(e.g., (111), (110), and (100)) have different atomic structures thatimpact any coating or hydroxylation of the surface. Prior to thedisclosure provided herein, these issues were not readily appreciatedwhen attempting to coat diamonds. These interfaces are commonlypresented from synthetic depositions of or preparations for diamond. Theorientation of the C—H or C—O axes and the relative corrugation aredifferent, and oxygen plasma alone may be insufficient to give both highcontact angles and abrasion resistance. Further complicating matters,this issue is especially problematic for gemstones (e.g., diamonds). Forinstance, gemstones are cut irrespective of these planes. In severalembodiments, the approaches disclosed herein provide reliable coverageand abrasion resistance by maximizing the number of hydroxyl species. Inseveral embodiments, a two-step process may be used. In severalembodiments, first, the diamond is treated with oxygen plasma orhydrogen plasma for cleaning and to increase number of C—Ox speciesand/or C—H species. In several embodiments, second, a water vapor annealprocess is performed to convert all C—H bonds to C—OH. In severalembodiments, a three-step process may be used. In several embodiments,first, the diamond is treated with oxygen plasma for cleaning and toincrease number of C—Ox species. In several embodiments, second, thediamond is treated with hydrogen plasma for a long duration to breakepoxides and maximize number of C—H bonds. In several embodiments,third, a water vapor anneal process is performed to convert all C—Hbonds to C—OH. In several embodiments, additional treatment steps may beused.

As disclosed elsewhere herein, in several embodiments, the substrate maybe a gemstone. In several embodiments, the process and monolayersdisclosed herein are especially useful for diamond surfaces (in view ofthe solutions to the problems disclosed elsewhere herein). Thus, diamondsurfaces are used throughout this disclosure as an exemplary embodiment(e.g., an exemplary substrate). Nonetheless, while several examples arediscussed using diamond as a reference substrate, the techniques andchemistry described herein can be adapted to other gemstones (e.g.,alexandrite, amethyst, aquamarine, citrine, diamond, emerald, garnet,jade, lapis lazuli, moonstone, morganite, onyx, opal, paraiba, pearls,peridot, rubellite, ruby, sapphire, spinel, tanzanite, topaz,tourmaline, turquoise, and zircon), other crystalline materials (e.g.SiC, synthetic diamond, CVD diamond wafer, etc.), other carbonaceousmaterials (e.g. carbide-derived carbon, carbonaceous aerogel,nanocrystalline diamond, graphitic carbon containing matrices, polymersubstrates, etc.), vitrified amorphous surfaces (e.g. diverse glasses,including crystal glass), polymers (e.g., polycarbonate glasses lens andsunglass lens), crystal glass, and the like.

The techniques and monolayer precursor molecules disclosed herein areespecially useful for substrates where optical properties are essentialand must be maintained in pristine condition (during use and/or througha coating process). The coatings disclosed herein are especially suitedto maintain or even improve the optical quality of the substrates theyare used to modify. The techniques and coatings disclosed herein may beused to render diamond jewelry, glasses lenses, sunglass lenses, watchfaces, spyglasses, gun scopes, periscopes, and the like soil-resistant(and/or fog resistant). In several embodiments, the substrate isconfigured for use as a lens (e.g., for viewing through). In severalembodiments, the substrate is polymer or glass. In several embodiments,the substrate is a magnifying lens (e.g., of a telescope, binoculars, ascope, etc.). In several embodiments, the polymer is a polycarbonate(e.g., a polycarbonate sunglass lens or glasses lens). In severalembodiments, the substrate is a glass (e.g., a glass sunglass lens orglass glasses lens). In several embodiments, the substrate is a crystalglass.

Surface-Functionalized Substrates and Their Methods of Manufacture andUse

As disclosed elsewhere herein, several embodiments pertain tosoil-resistant coatings on substrates. In several embodiments, thecoating (e.g., monolayer coating) changes the natural surface chemistryof the substrate surface (e.g., diamond surface) and/or the physicalproperties of the substrate surface (e.g., diamond surface) to which thecoating is bonded. As disclosed elsewhere herein, diamonds (and/or someother gemstones or substrates) are largely chemically inactive, makingit difficult to coat them to prevent soiling. Until now, techniques toattach a physical coating directly to a diamond surface have beenlargely ineffective. For instance, the largely inert surface of adiamond may resist interaction with a reactive monolayer precursormolecule. As noted elsewhere herein, the diamond surface has anabundance of groups that are not reactive to coating materials (e.g.,silanizing groups). Thus, during coating, bare spots and/or irregularsurfaces may be left, frustrating the purpose of coating the diamond inthe first place. This problem associated with diamond coatings (andcoatings for other substrates) or others are addressed herein.

Additionally, this lack of sufficient and/or adequate reactivity is alsoan issue for diamonds that have been plasma treated. While plasmatreating improves coating efficiency on diamonds (and some othersubstrates), plasma treating itself is not to a sufficient degree toavoid bare spots and/or irregularities within the coating. Thus, thediamond can still attract dirt and grime readily. In some embodimentsdisclosed herein, the surface of a diamond (or other gemstone orsubstrate) is subject to a two-or-more step process to prepare and/orchange the surface, thereby conferring reactivity to the surface. Forinstance, a diamond (or other substrate) may be plasma treated toincrease the amount of reactive and/or nucleophilic groups on thesurface of the diamond (or other substrate). Thereafter, the substratesurface is annealed to further increase the amount of reactive specieson the surface (e.g., reactive oxygen species).

As disclosed elsewhere herein, the plasma treatment process may beperformed using oxygen, hydrogen, or both (in different treatmentsteps). Argon may also be used in combination with either oxygen orhydrogen. Because the molecular speed of hydrogen gas is low (due to itslow mass), in several embodiments, argon gas is used simultaneously withhydrogen. Alternatively, argon maybe used to purge the plasma chamber toensure hydrogen gas is pumped out of the chamber after plasma treatmentof an article within the chamber (e.g., a diamond, lens, etc.). Inseveral embodiments, different cycles of plasma gas may be used duringplasma treatment. For example, in several embodiments, plasma treatmentmay include exposure of the article to oxygen plasma, followed byhydrogen plasma. In other embodiments, plasma treatment may includeexposure of the article to hydrogen plasma, followed by oxygen plasma.In several embodiments, plasma treatment may include exposure of thearticle may include exposure to high pressure oxygen plasma followed, bylow pressure oxygen plasma, followed by low pressure hydrogen plasma. Inseveral embodiments, plasma treatment may include exposure of thearticle to oxygen plasma, followed by hydrogen plasma. Othercombinations are possible. In several embodiments, plasma treatment mayinclude exposure of the article to multiple hydrogen plasma treatments,multiple oxygen plasma treatments, or multiple hydrogen and oxygenplasma treatments (performed sequentially).

In several embodiments, during plasma treatment, an article to betreated is placed in a plasma treatment chamber. In several embodiments,a plasma gas (e.g., oxygen, hydrogen, combinations of the foregoing withargon, etc.) is fed into the plasma chamber. In several embodiments, theplasma generator generates plasma by exposing the plasma gas toelectrical power of equal to or greater than about: 50 W, 100 W, 150 W,200 W, or ranges including and/or spanning the aforementioned values. Inseveral embodiments, where different plasma treatment steps areperformed (e.g., a first and second plasma treatment step using oxygenand hydrogen, respectively), different electrical power levels may beused. For example, the first plasma treatment may be performed at onepower, and the second at a second higher power. In several embodiments,the electrical power for the first treatment is equal to or less thanabout: 50 W, 100 W, 150 W, or ranges including and/or spanning theaforementioned values. In several embodiments, the electrical power forthe second treatment is equal to or less than about: 100 W, 150 W, 200W, or ranges including and/or spanning the aforementioned values.

In several embodiments, the flow rate of the plasma gas may becontrolled. In several embodiments, the flow rate of gas is equal to orless than about: 1 standard cubic centimeters per minute (sccm), 5 sccm,10 sccm, 15 sccm, 20 sccm, 25 sccm, 30 sccm, 50 sccm, 75 sccm, 100 sccm,or ranges including and/or spanning the aforementioned values. Inseveral embodiments, where different plasma treatment steps areperformed (e.g., a first and second plasma treatment step using oxygenand hydrogen, respectively), different flow rates may be used. Forexample, the first plasma treatment may be performed at one flow rateand the second at a second flow rate. In several embodiments, the firstflow rate is slower than the second. In other embodiments, the firstflow rate is faster than the second. In several embodiments, the firstflow rate of gas is equal to or less than about: 1 standard cubiccentimeters per minute, 5 sccm, 10 sccm, 15 sccm, 20 sccm, 25 sccm, 30sccm, 50 sccm, 75 sccm, 100 sccm, or ranges including and/or spanningthe aforementioned values. In several embodiments, the second flow rateof gas is equal to or less than about: 1 standard cubic centimeters perminute (sccm), 5 sccm, 10 sccm, 15 sccm, 20 sccm, 25 sccm, 30 sccm, 50sccm, 75 sccm, 100 sccm, or ranges including and/or spanning theaforementioned values.

In several embodiments, the gas pressure used during plasma treatmentcan be higher or lower depending on the desired result. In severalembodiments, higher gas pressures may be used when faster plasmatreatment times are desired. In several embodiments, the gas pressureduring plasma treatment is equal to or less than about: 100 mtorr, 200mtorr, 300 mtorr, 320 mtorr, 350 mtorr, 400 mtorr, 600 mtorr, or rangesincluding and/or spanning the aforementioned values. In severalembodiments, where different plasma treatment steps are performed (e.g.,a first and second plasma treatment step using oxygen and hydrogen,respectively), different pressure levels may be used. For example, thefirst plasma treatment may be performed at one pressure, and the secondat a second pressure.

In several embodiments, the duration of plasma treatment can be adjusteddepending on the article being treated. In several embodiments, theduration of plasma treatment is equal to or less than about: 2 minutes,10 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, or rangesincluding and/or spanning the aforementioned values. In severalembodiments, where different plasma treatment steps are performed (e.g.,a first and second plasma treatment step using oxygen and hydrogen,respectively), different exposure times may be used. For example, thefirst plasma treatment may be performed for one period of time, and thesecond for a second period of time. In several embodiments, the firstperiod of time is shorter than the second. In other embodiments, thefirst period of time is longer than the second. In several embodiments,the duration of plasma treatment for the first period of time is equalto or less than about: 2 minutes, 10 minutes, 20 minutes, 30 minutes, orranges including and/or spanning the aforementioned values. In severalembodiments, the duration of plasma treatment for the second period oftime is equal to or less than about: 20 minutes, 30 minutes, 45 minutes,1 hour, or ranges including and/or spanning the aforementioned values.

In several embodiments, as shown in FIGS. 2A, 2B, and 5 , the surface ofa raw substrate or raw diamond comprises hydroxyl groups, carbonylgroups, carboxylic acid groups, epoxide groups, C—H groups, and C—Cgroups. These hydroxyl groups, carbonyl groups, carboxylic acid groups,epoxide groups, C—H groups, and C—C groups are represented using adiamond surface, Surface (I-r), using groups A¹, A², A³, A⁴, A⁵, and A⁶,respectively:

In several embodiments, the precursor substrate surface (e.g., theprecursor diamond surface) comprises additional reactive oxygen speciesrelative to the raw substrate surface (e.g., the raw diamond surface).For instance, the ratio of reactive oxygen species, A¹ and/or A³(hydroxyl groups and/or carboxylic acid groups, respectively), relativeto a total number of surface groups, A¹ to A⁶, may be increased afterplasma treatment. In several embodiments, the ratio of reactive oxygenspecies is quantitatively calculated as (A¹)/(A¹+A²+A³+A⁴+A⁵+A⁶), as(A³)/(A¹+A²+A³+A⁴+A⁵+A⁶), or as (A¹+A³)/(A¹+A²+A³+A⁴+A⁵+A⁶). The(A¹)/(A¹+A²+A³+A⁴+A⁵+A⁶) may be abbreviated using the following termRatio^(Precursor(1)) (where the substrate surface and ratio beingindicated is provided as a superscript on “Ratio”). Similarly, the ratioof A³ groups to total groups on the precursor surface may be expressedas Ratio^(Precursor(3)). Likewise, the ratio of A¹ and A³ groups tototal groups on the precursor surface may be expressed asRatio^(Precursor(1,3)). This same naming convention may be used for theraw substrate by replacing the term “Precursor” in the superscript withthe term “Raw” (e.g., Ratio^(Raw(1)), Ratio^(Raw(1)), Ratio^(Raw(1))).In several embodiments, this ratio is quantitively determined (e.g.,using spectroscopy, such as XPS (X-ray photoelectron spectroscopy)). Inseveral embodiments, this ratio is qualitatively calculated (e.g., usingFT-IR (Fourier transform infrared), FTIR ATR (attenuated total internalreflectance) spectroscopy, or other spectroscopic techniques). Forexample, the height and/or area of representative peaks may be compared(e.g., indicative C—OH peaks, C═O peaks, C—O—C peaks, C—H peaks, etc.).

In several embodiments, the ratio of A¹ and/or A³ groups relative to atotal number of surface groups A¹ to A⁶ for the precursor surface (e.g.,precursor diamond surface) is higher than the ratio of A¹ and/or A³groups relative to a total number of surface groups A¹ to A⁶ for the rawsubstrate surface (e.g., raw diamond surface). For example, any one ormore of the following may be true: Ratio^(Prrecursor(1))>Ratio^(Raw(1)),Ratio^(Precursor(3))>Ratio^(Raw(3)),Ratio^(Precursor(1,3))>Ratio^(Raw(1,3)). In several embodiments, afterconversion to the precursor surface (e.g., the precursor diamondsurface), the amount of reactive oxygen species (e.g., A¹ groups, A³groups, and/or both) of the surface is increased by equal to or at leastabout: 10%, 25%, 50%, 100%, 150%, 200%, 300%, or ranges including and/orspanning the aforementioned values.

In several embodiments, the increase in the ratio of reactive groupsincreases the hydrophilicity of the precursor surface relative to theraw surface. In several embodiments, a contact angle for water on theraw surface is equal to or at least about: 30°, 40°, 50°, 60°, 70°, 80°,90°, 100°, or ranges including and/or spanning the aforementionedvalues. In several embodiments, a contact angle for water on theprecursor surface is equal to or at least about: 25°, 30°, 40°, 50°,60°, 70°, 80°, 90°, or ranges including and/or spanning theaforementioned values. In several embodiments, after conversion to theprecursor surface, the water contact angle of the substrate surface islowered (relative to the raw surface) by equal to or at least about:2.5%, 5%, 10%, 15%, 20%, 50%, 75%, or ranges including and/or spanningthe aforementioned values.

In several embodiments, the increase in the ratio of reactive groupsincreases the hydrophilicity of the precursor diamond surface relativeto the raw diamond surface. In several embodiments, a contact angle forwater on the raw diamond surface is equal to or at least about: 40°,50°, 60°, 70°, 80°, 90°, or ranges including and/or spanning theaforementioned values. In several embodiments, a contact angle for wateron the precursor diamond surface is equal to or at least about: 25°,30°, 40°, 50°, 60°, 70°, 80°, or ranges including and/or spanning theaforementioned values. In several embodiments, after conversion to theprecursor diamond surface, the water contact angle of the diamondsurface (e.g., the raw diamond surface) is lowered by equal to or atleast about: 2.5%, 5%, 10%, 15%, 20%, 50%, 75%, or ranges includingand/or spanning the aforementioned values.

In several embodiments, the plasma treated article (e.g., diamond orsome other article) is thereafter annealed to provide additionalreactive groups on the surface. In several embodiments, as shown inFIGS. 2A and 2B, plasma treatment of a substrate generates additionalreactive species on the substrate (FIG. 2A) and the diamond (FIG. 2B)(see also, FIG. 5 ). As shown in FIGS. 2A and 2B, the plasma treatmentin Step A provides a Precursor Surface and a Precursor Diamond Surface,respectively. In several embodiments, the reactive groups of thePrecursor Surface and Precursor Diamond Surface include —OH groups andcarboxylic acid groups (e.g., reactive oxygen species) at the surface ofthe substrate or diamond (or other substrate). In several embodiments,these reactive oxygen groups are nucleophilic. By annealing, additionaland more regularly distributed reactive oxygen species are provided onthe substrate surface (as shown in FIGS. 2A and 2B as the ReactiveSurface and Reactive Diamond Surface, generated in Step B).

In several embodiments, the procedures disclosed herein, including theplasma treatment processes disclosed herein, increase the relative ratioof —OH species (A¹ groups) on the surface of the substrate. In severalembodiments, this provides a more regular bonding surface with strongerbonding to the silanizing agent than surfaces where the ratio of—C(═O)OH is higher (though carboxylic acid groups (e.g., A³ groups) arestill somewhat reactive to silanizing agents). In several embodiments,by increasing the ratio of hydroxyl species, longer lasting, moredurable, and/or more soil-resistant surfaces are provided.

In several embodiments, as disclosed elsewhere herein, an annealingprocess is performed using water (e.g., water vapor). In severalembodiments, annealing further increases the relative ratio of —OHspecies (A¹ groups) on the surface of the substrate. In severalembodiments, water is provided in a carrier gas (e.g., nitrogen, argon,etc.) to anneal the surface of the substrate (e.g., diamond surface).

In several embodiments, the annealing process preformed using heat. Inseveral embodiments, as shown in FIG. 3 , the annealing process maycomprise flowing an inert gas (e.g., nitrogen) through water to providewater vapor in the gas. In several embodiments, the annealing process isperformed using heat by placing the substrate in heater (e.g., afurnace) as it is exposed to water vapor. In several embodiments, theannealing process is performed at a temperature equal to or at leastabout: 300° C., 400° C., 450° C., 500° C., 550° C., 600° C., or rangesincluding and/or spanning the aforementioned values.

In several embodiments, the reactive substrate surface (e.g., thereactive diamond surface) comprises additional reactive oxygen speciesrelative to the precursor surface and/or the raw substrate surface(e.g., the precursor or raw diamond surface). For instance, the ratio ofreactive oxygen species, A¹ and/or A³, relative to a total number ofsurface groups, A¹ to A⁶, may be increased after annealing. As above,the ratio of reactive oxygen species may be expressed asRatio^(Reactive(1)), Ratio^(Reactive(3)), and/or Ratio^(Reactive(1,3)).In several embodiments, this ratio is qualitatively calculated (e.g.,using FT-IR, FTIR ATR, spectroscopy, or other spectroscopic techniques).For example, the height and/or area of representative peaks may becompared.

In several embodiments, the ratio of A¹ and/or A³ groups relative to atotal number of surface groups A¹ to A⁶ for the reactive surface (e.g.,reactive diamond surface) is higher than the ratio of A¹ and/or A³groups relative to a total number of surface groups A¹ to A⁶ for the rawsubstrate surface (e.g., raw diamond surface). For example, any one ormore of the following may be true: Ratio^(Reactive(1))>Ratio^(Raw(1)),Ratio^(Reactive(3))>Ratio^(Raw(3)),Ratio^(Reactive(1,3))>Ratio^(Raw(1,3)). In several embodiments, afterconversion to the reactive surface (e.g., the reactive diamond surface),the amount of reactive oxygen species (e.g., A¹ groups, A³ groups,and/or both) of the surface relative to that of the raw surface (e.g.,the raw diamond surface) is increased by equal to or at least about:10%, 25%, 50%, 100%, 150%, 200%, 300%, 400%, or ranges including and/orspanning the aforementioned values.

In several embodiments, the ratio of A¹ and/or A³ groups relative to atotal number of surface groups A¹ to A⁶ for the reactive surface (e.g.,reactive diamond surface) is higher than the ratio of A¹ and/or A³groups relative to a total number of surface groups A¹ to A⁶ for theprecursor substrate surface (e.g., precursor diamond surface). Forexample, any one or more of the following may be true:Ratio^(Reactive(1))>Ratio^(Precursor(1)),Ratio^(Reactive(3))>Ratio^(Precursor(3)),Ratio^(Reactive(1,3))>Ratio^(Precursor(1,3)). In several embodiments,after conversion to the reactive surface (e.g., the reactive diamondsurface), the amount of reactive oxygen species (e.g., A¹ and/or A³groups) of the surface relative to that of the precursor surface (e.g.,the precursor diamond surface) is increased by equal to or at leastabout: 10%, 25%, 50%, 100%, 150%, 200%, 300%, or ranges including and/orspanning the aforementioned values.

In several embodiments, the increase in the ratio of reactive groupsincreases the hydrophilicity of the reactive surface (e.g., reactivediamond surface) relative to the precursor surface (e.g., precursordiamond surface). In several embodiments, a contact angle for water onthe precursor surface (e.g., precursor diamond surface) is equal to orat least about: 25°, 30°, 40°, 50°, 60°, 70°, 80°, or ranges includingand/or spanning the aforementioned values. In several embodiments, acontact angle for water on the reactive surface (e.g., reactive diamondsurface) is equal to or at least about: 5°, 10°, 20°, 30°, 40°, 50°,60°, 70°, or ranges including and/or spanning the aforementioned values.In several embodiments, after conversion to the reactive surface (e.g.,reactive diamond surface), the water contact angle of the substratesurface is lowered, relative to the precursor surface (e.g., precursordiamond surface), by equal to or at least about: 10%, 20%, 30%, 40%,50%, 60%, 70%, 80%, 90%, 95%, 99%, or ranges including and/or spanningthe aforementioned values.

In several embodiments, after pretreatment, nucleophilic groups on thesurface of the substrate (e.g. diamond) can be functionalized. Inseveral embodiments, the nucleophilic groups on the reactive surface ofthe substrate are functionalized using a silanizing group. Thesilanizing group is a monolayer precursor molecule. In severalembodiments, the silanizing group may include halo-silane (e.g.,Si(X^(H))₃—R, Si(X^(H))₂—R₂, Si(X^(H))—R₃, etc., where R is a tail),hydride-silane (e.g., SiH₃—R, SiH₂—R₂, SiH—R₃, etc., where R is a tail),or alkoxysilane (e.g., Si(—O-alkyl)₃-R, Si(—O-alkyl)₂-R₂,Si(—O-alkyl)-R₃, etc., where R is a tail). Such a functionalization isshown in Step C of FIGS. 2A and 2B. The functionalization is also shownin FIG. 5 .

In several embodiments, by functionalizing the nucleophilic groups ofthe substrate using a silanizing group, the substrate (e.g., diamond,lens, etc.) becomes functionalized with a silane unit. In this way, asubstrate (e.g., diamond, gemstone, lens, etc.) with an anti-foulingand/or soil resistant coating can be prepared. In several embodiments,the silane unit-coated substrate (e.g., diamond, lens, etc.) is adaptedto repel grease and grime. In several embodiments, this modificationresults in a functionalized substrate (e.g., diamond, lens, etc.) thatrepels dirt and oil for longer periods and prevents and/or slows thesoiling of the substrate surface (e.g., diamond, gemstone, glass, lens,or polycarbonate surface). In several embodiments, the functionalizedsubstrate (e.g., diamond, lens, etc.) is hydrophobic (repels aqueousliquids, including water). In several embodiments, the coated surface ofthe diamond is amphiphobic (repels both oils and water). In severalembodiments, a contact angle for canola oil or olive oil on the coatedsurface (e.g., coated diamond surface) is equal to or at least about:45°, 50°, 60°, 70°, 80°, 90°, 100°, or ranges including and/or spanningthe aforementioned values.

In several embodiments, as disclosed elsewhere herein, the anti-soilingand/or soil-resistant surface coating is covalently bonded to thesubstrate (e.g., diamond). In several embodiments, the anti-soilingsurface coating comprises, consists of, or consists essentially of amonolayer. In several embodiments, the substrate surface and monolayeris represented by Surface (I):

In several embodiments, n is an integer equal to or less than about: 0,1, 2, 3, 4, 5, 6, 7, 8, or ranges including and/or spanning theaforementioned values. For example, in several embodiments, n is aninteger ranging from 0 to 10, from 0 to 8, from 0 to 6, or from 0 to 4.To further illustrate, in several embodiments, n is an integer selectedfrom 0, 1, 2, 3, or 4. In several embodiments, m is an integer equal toor less than about: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, orranges including and/or spanning the aforementioned values. For example,in several embodiments, m is an integer ranging from 1 to 15, from 1 to20, from 6 to 8, from 6 to 10, or from 6 to 12. In several embodiments,m is equal to or greater than about: 6, 7, 8, 9, 10, 11, or 12. Inseveral embodiments, n is 2. In several embodiments, m is between 6 and12. In several embodiments, m is 8. In several embodiments, the “S-unit”is a silane unit. In several embodiments, a collection of S-unitsprovide a monolayer. In several embodiments, the Surface is a substratesurface. In several embodiments, the surface is a diamond surface. Inother embodiments, the Surface may be that of another gemstone. Inseveral embodiments the Surface is glass, a polymer surface, etc. Inseveral embodiments, the Surface is the surface of a watch face, is aglasses lens, a sunglass lens, or a magnifying lens.

It will be appreciated that Surface (I) provides a representativeexample showing that each Si atom may bond to an adjacent Si atom andthe substrate to provide a monolayer spanning the surface. Instead ofbeing covalently bonded to two adjacent Si atoms, certain Si atoms mayhave additional bonds to the substrate surface (e.g., through hydroxylgroups). Such an embodiment is shown below (and elsewhere herein inSurface (IV)). In several embodiments, a Si atom in the monolayer canhave 1, 2, or 3 to the substrate itself (e.g., through a hydroxylgroup). Thus, any of the following (Si-Attachment) arrangements ispossible for any of the Surface representations provided herein. The “

” portions in the following structures indicate bonding through an —O—to an adjacent Si atom. For instance, Si-Attachment “A” is as shown inSurface (I). However, the S-units of Surface (I) (or any other surfacedisclosed herein, including, Surface (I-i), (II), (III), (IV), (IV-i))can be replaced by Si-Attachment B, C, D, or E.

As disclosed elsewhere herein, in several embodiments, each “S-unit”represents a silane unit. In several embodiments, the silane unitcomprises Si(CH₂)_(n)(CF₂)_(m)CF₃. In several embodiments, each S-unitcomprises a tail (e.g., a soil resistant tail). In several embodiments,the tail (e.g., a soil resistant tail) of the S-unit confers soilresistant properties on the surface (when combined with other S-units).In several embodiments, each nm² of the soil resistant surface (e.g.,soil resistant diamond surface) comprises equal to or at least about: 1S-unit, 2 S-unit, 3 S-unit, or ranges including and/or spanning theaforementioned values. In several embodiments, each nm² of the soilresistant surface (e.g., soil resistant diamond surface) comprises equalto or at least about: 1 tail, 2 tails, 3 tails, or ranges includingand/or spanning the aforementioned values.

In several embodiments, the Surface (I) is further represented bySurface (I-i):

where n is 2 and m is 7. In several embodiments, definitions for likevariables in different formulae (n for Formula (I) and Formula (II),etc.) maybe used to define that like variable for any other formulawhere the variable occurs. Thus, any definition of a variable forFormula (I) may be defined using that same variable for any one or moreof Formula (I-i), (II), (III), and (IV), (or vice versa).

In several embodiments, the substrate surface and monolayer isrepresented by Surface (II):

where variables are as disclosed elsewhere herein and X is —O—, —NH—, or—CF₂—. In several embodiments, n is an integer equal to or less thanabout: 0, 1, 2, 3, 4, 5, 6, 7, 8, or ranges including and/or spanningthe aforementioned values. In several embodiments, m is an integer equalto or less than about: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20,21, or ranges including and/or spanning the aforementioned values. Inseveral embodiments, Surface (II) is represented by Surface (I) when Xis —CF₂—.

In several embodiments, the substrate surface and monolayer isrepresented by Surface (III):

In several embodiments, alkyl is as disclosed elsewhere herein. Inseveral embodiments, the alkyl in Formula (III) is optionallysubstituted C₁ to C₈ alkyl. In several embodiments, the alkyl in Formula(III) is optionally substituted C₁ to C₆ alkyl. In several embodiments,the alkyl in Formula (III) is optionally substituted C₁ to C₄ alkyl. Inseveral embodiments, the alkyl in Formula (III) is optionallysubstituted C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, or C₁₀ alkyl. In severalembodiments, the alkyl in Formula (III) is branched. In severalembodiments, the alkyl in Formula (III) is —(CH₂)_(n)—. In severalembodiments, haloalkyl is as disclosed elsewhere herein. In severalembodiments, the haloalkyl in Formula (III) is optionally substituted C₁to C₂₀ haloalkyl. In several embodiments, the haloalkyl in Formula (III)is optionally substituted C₁ to C₁₂ haloalkyl. In several embodiments,the haloalkyl in Formula (III) is optionally substituted C₁ to C₆haloalkyl. In several embodiments, the alkyl in Formula (III) isoptionally substituted C₆ to C₁₂ haloalkyl. In several embodiments, thehaloalkyl in Formula (III) is optionally substituted C₁, C₂, C₃, C₄, C₅,C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, haloalkyl. In several embodiments, thehaloalkyl in Formula (III) is branched. In several embodiments, thehaloalkyl in Formula (III) is —(CF₂)_(m)—CF₃. In several embodiments,haloalkyl is fluoroalkyl. In several embodiments, haloalkyl isperfluoroalkyl. In several embodiments, X is —O—, —NH—, or —CF₂—. Inseveral embodiments, n is an integer equal to or less than about: 0, 1,2, 3, 4, 5, 6, 7, 8, or ranges including and/or spanning theaforementioned values. In several embodiments, m is an integer equal toor less than about: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20,21, or ranges including and/or spanning the aforementioned values. Inseveral embodiments, Surface (III) may be represented by Surface (I),(I-i), or (II). Alternatively, the Si bonding to the substrate surfacemay be represented by

In several embodiments, the substrate surface and monolayer isrepresented by Surface (IV):

In several embodiments, Surface (IV) may be represented by any one ofSurfaces (I), (II) or (III). For instance, in several embodiments, the“soil-resistant-tail” is represented by -alkyl-X-haloakyl. In severalembodiments, the “soil-resistant-tail” is an optionally substitutedalkyl. In several embodiments, the “soil-resistant-tail” is anoptionally substituted haloalkyl. In several embodiments, the“soil-resistant-tail” is represented by -alkyl-haloakyl. In severalembodiments, the “soil-resistant-tail” is represented by—(CH₂)_(n)—X—(CF₂)_(m)—CF₃. In several embodiments, the“soil-resistant-tail” is represented (or comprises) by—(CH₂)_(n)—(CF₂)_(m)—CF₃. In several embodiments, the“soil-resistant-tail” is a substituent selected from the groupconsisting of heptafluoroisopropoxypropyl, heptafluoroisopropoxypropyl-,bis(nonafluorohexyldimethylsiloxy)methyl-silylethyl-,tridecafluoro-2-(tridecafluorohexyl)decyl-,heneicocyl-1,1,2,2-tetrahydrodecyl-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)methyl-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)-,(tridecafluoro-1,1,2,2-tetrahydrooctyl)-,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-, and combinations of any ofthe foregoing.

In several embodiments, the substrate surface and monolayer isrepresented by Surface (IV-i):

In several embodiments, p is an integer selected from 1, 2, or 3. Inseveral embodiments, Surface (IV-i) may be represented by any one ofSurfaces (I), (II) or (III), where p is 1. Surface (IV-i) represents aconfiguration where the Si atom includes one or more tails (e.g., 1, 2,or 3). In several embodiments, each instance of the“soil-resistant-tail” is independently represented by -alkyl-X-haloakyl.In several embodiments, each instance of the “soil-resistant-tail” isindependently represented by —(CH₂)_(n)—X—(CF₂)_(m)—CF₃. In severalembodiments, each instance of the “soil-resistant-tail” is independentlyrepresented by —(CH₂)_(n)—(CF₂)_(m)—CF₃.

Several embodiments pertain to a soil resistant substrate (e.g.,diamond, lens, etc.) prepared by a method as disclosed elsewhere herein.Several embodiments pertain to a method of preparing a soil resistantsubstrate (e.g., a soil resistant diamond, lens, etc.). In severalembodiments, as disclosed elsewhere herein and as shown in FIGS. 2A, 2Band 5 , a soil resistant substrate (e.g., diamond or other substrate) isprepared by plasma treating a surface of a raw substrate (e.g., diamondsurface) to provide a precursor surface (of the substrate, e.g.,diamond, etc.) having a precursor surface (e.g., a precursor diamondsurface). In several embodiments, as disclosed elsewhere herein, theprecursor surface (e.g., precursor diamond surface) is chemicallydifferent than the surface of the raw substrate (e.g., the raw diamond).In several embodiments, as disclosed elsewhere herein, the precursorsurface (e.g., precursor diamond surface) has different physicalproperties than the surface of the raw substrate (e.g., the rawdiamond).

In several embodiments, the method comprises annealing the precursorsurface (e.g., precursor diamond surface) to provide a reactivesubstrate surface (e.g., reactive diamond surface). In severalembodiments, the reactive surface (e.g., reactive diamond surface) ischemically different from the precursor surface (e.g., the precursordiamond surface). In several embodiments, the reactive substrate surface(e.g., reactive diamond surface) is physically different than theprecursor surface. In several embodiments, the reactive substratesurface has sufficient density of reactive groups to provide asoil-resistant layer and/or coating substantially free from defects. Inseveral embodiments, the reactive substrate surface has a density ofreactive groups (e.g., reactive oxygen species) that is equal to or atleast about: 1 reactive group per nm², 2 reactive groups per nm², 3reactive groups per nm², 4 reactive groups per nm², or ranges includingand/or spanning the aforementioned values.

In several embodiments, as disclosed elsewhere herein, to prepare thecoated surface, a reactive substrate surface (e.g., reactive diamondsurface) is exposed to a silanizing agent (e.g., silanizing group)comprising an S-unit. In several embodiments, the silanizing agent(e.g., silanizing group) comprises the following structure:(LG)₃Si-(soil-resistant-tail), where the soil-resistant-tail is asdisclosed elsewhere herein. In several embodiments, each instance of LGis a leaving group independently selected from alkyl, alkoxy, and ahalogen. In several embodiments, the silanizing agent comprises thefollowing structure: (LG)₃Si-alkyl-X-haloalkyl, where X, alkyl, andhaloalkyl are as disclosed elsewhere herein. In several embodiments, thesilanizing agent comprises the following structure:(LG)₃Si(CH₂)_(n)—X—(CF₂)_(m)CF₃. In several embodiments, each of “X”,“n”, and “m” are as disclosed elsewhere herein. In several embodiments,the silanizing agent comprises the following structure:(LG)₃Si(CH₂)_(n)(CF₂)_(m)CF₃.

In several embodiments, the silanizing group (e.g., silanizing agent) isselected from the group consisting ofheptafluoroisopropoxypropyltrichlorosilane,heptafluoroisopropoxypropyltrimethoxysilane,bis(nonafluorohexyldimethylsiloxy)methyl-silylethyldimethylchlorosilane,tridecafluoro-2-(tridecafluorohexyl)decyltrichlorosilane,heneicocyl-1,1,2,2-tetrahydrodecyltrichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)methyldichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyldichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, andcombinations of any of the foregoing.

In several embodiments, the anti-soiling coating is durable. In severalembodiments, the contact angle of the anti-soiling coating remainswithin 10% of its original value after equal to or at least about: 50abrasion cycles, 100 abrasion cycles, 200 abrasion cycles, or rangesincluding and/or spanning the aforementioned values. In severalembodiments, the contact angle of the anti-soiling coating remainswithin 5%, 10%, 15%, or 20% (or ranges including and/or spanning theaforementioned values) of its original value after equal to or at leastabout 50 abrasion cycles, 100 abrasion cycles, 200 abrasion cycles, orranges including and/or spanning the aforementioned values. An abrasioncycle is performed by rubbing a substrate against a cotton cloth in aforward and backward direction a distance of 10 substrate lengths (e.g.,10 cm for a 1 cm substrate) in each direction (as disclosed in theExamples). In several embodiments, the abrasion cycle is performed usingslight finger pressure (sufficient to allow movement of the substrateagainst the cloth without the cloth slipping away from the substrate orfinger).

In several embodiments, the treated gemstones (e.g., molecularlyfunctionalized diamonds) disclosed herein retain their brilliance, fire,luster, and scintillation for longer periods of time (e.g., for days,weeks longer, and months longer) than untreated gemstones. Moreover,whereas the current mechanical or chemical cleaning methods do notcompletely remove all contaminants, the molecular layers as disclosedherein protect the gemstone surface from grease accumulation, grantingoptical quality.

Surprisingly, in several embodiments, it has been found that thebrilliance, fire, luster, and/or scintillation is not significantlyaffected by silanization with a silane unit. In several embodiments, anydecrease in the brilliance, fire, luster, and/or scintillation isimperceptible to a trained jeweler using their naked eye or an eyeloupe. In several embodiments, any decrease in the brilliance, fire,luster, and/or scintillation may be measured spectroscopically (usinglight intensity measures, absorption, transmittance, etc.). In severalembodiments, after functionalization with a silane unit as disclosedelsewhere herein, the functionalized (e.g., silanized) diamond'sbrilliance is decreased relative to the raw diamond by less than orequal to about: 15%, 10%, 5%, 2.5%, 1.0%, 0%, or ranges including and/orspanning the aforementioned values. In several embodiments, afterfunctionalization with a silane unit as disclosed elsewhere herein, thefunctionalized (e.g., silanized) diamond's fire is decreased relative tothe raw diamond by less than or equal to about: 15%, 10%, 5%, 2.5%,1.0%, 0%, or ranges including and/or spanning the aforementioned values.In several embodiments, after functionalization with a silane unit asdisclosed elsewhere herein, the functionalized (e.g., silanized)diamond's luster is decreased relative to the raw diamond by less thanor equal to about: 15%, 10%, 5%, 2.5%, 1.0%, 0%, or ranges includingand/or spanning the aforementioned values. In several embodiments, afterfunctionalization with a silane unit as disclosed elsewhere herein, thefunctionalized (e.g., silanized) diamond's scintillation is decreasedrelative to the raw diamond by less than or equal to about: 15%, 10%,5%, 2.5%, 1.0%, 0%, or ranges including and/or spanning theaforementioned values.

Surprisingly, in certain implementations, it has been found that thebrilliance, fire, luster, and/or scintillation is improved aftersilanization with a silane unit.

In several embodiments, the treated gemstones (e.g., diamonds) retainshowroom quality shine under normal wearing conditions for a period ofat least about: 1 week, 2 weeks, a month, 3 months, 6 months, or rangesincluding and/or spanning the aforementioned values. This surprising andunexpected improvement is significant considering that untreateddiamonds begin to accumulate matter that dulls their appearancesubstantially immediately after cleaning.

In several embodiments, a treated substrate (e.g., coated substrate,such as a diamond) retains equal to or at least about: 70%, 80%, 90%,95%, 99%, or 100% (or ranges including and/or spanning theaforementioned values) of its brilliance under normal wearing conditionsfor a given period of time. In several embodiments, relative to anatural gemstone (e.g., a natural diamond), the brilliance of thetreated gemstone (e.g., diamonds) is improved by: 1.0%, 2.5%, 5.0%, 10%,20%, 30%, 40%, or 50% (or ranges including and/or spanning theaforementioned values) under equivalent normal wearing conditions for agiven period of time. For instance, if a treated diamond and untreateddiamond are placed in substantially equivalent wear conditions and,after a given period of wear of one month, if the brilliance of thenormal diamond has decreased and the brilliance of the treated diamondhas decreased to a smaller degree, this would be quantified as animprovement in brilliance for the treated diamond. If the brilliance ofthe untreated diamond decreased by 35%, but the brilliance of thetreated diamond only decreased by 5%, this would be quantified as a 30%improvement in brilliance over the given period of time (one month). Inseveral embodiments, the period of time after which brilliance ismeasured is a period of equal to or at least about: 1 week, 2 weeks, amonth, 2 months, 3 months, or ranges including and/or spanning theaforementioned values.

In several embodiments, a treated gemstone (e.g., coated gemstone ordiamond) retains equal to or at least about: 70%, 80%, 90%, 95%, 99%, or100% (or ranges including and/or spanning the aforementioned values) ofits fire under normal wearing conditions for a given period of time. Inseveral embodiments, relative to a natural gemstone (e.g., a naturaldiamond), the fire of the treated gemstone (e.g., diamonds) is improvedby: 2.5%, 5.0%, 10%, 20%, 30%, 40%, or 50% (or ranges including and/orspanning the aforementioned values) under equivalent normal wearingconditions for a given period of time. For instance, if a treateddiamond and untreated diamond are placed in substantially equivalentwear conditions and, after a given period of wear of one month, if thefire of the normal diamond has decreased and the fire of the treateddiamond has decreased to a smaller degree, this would be quantified asan improvement in fire for the treated diamond. If the fire of theuntreated diamond decreased by 35%, but the fire of the treated diamondonly decreased by 5%, this would be quantified as a 30% improvement infire over the given period of time (one month). In several embodiments,the period of time after which fire is measured is a period of equal toor at least about: 1 week, 2 weeks, a month, 2 months, 3 months, orranges including and/or spanning the aforementioned values.

In several embodiments, a treated substrate (e.g., coated substrate,coated diamond, etc.) retains equal to or at least about: 70%, 80%, 90%,95%, 99%, or 100% (or ranges including and/or spanning theaforementioned values) of its clarity under normal wearing conditionsfor a given period of time. In several embodiments, relative to anatural gemstone (e.g., a natural diamond), the clarity of the treatedgemstone (e.g., diamonds) is improved by: 2.5%, 5.0%, 10%, 20%, 30%,40%, or 50% (or ranges including and/or spanning the aforementionedvalues) under equivalent normal wearing conditions for a given period oftime. For instance, if a treated diamond and untreated diamond areplaced in substantially equivalent wear conditions and, after a givenperiod of wear of one month, if the clarity of the normal diamond hasdecreased and the clarity of the treated diamond has decreased to asmaller degree, this would be quantified as an improvement in clarityfor the treated diamond. If the clarity of the untreated diamonddecreased by 35%, but the clarity of the treated diamond only decreasedby 5%, this would be quantified as a 30% improvement in clarity over thegiven period of time (one month). In several embodiments, the period oftime after which clarity is measured is a period of equal to or at leastabout: 1 week, 2 weeks, a month, 2 months, 3 months, or ranges includingand/or spanning the aforementioned values.

In several embodiments, where the substrate is clear or transparent(e.g., a glasses lens, diamond, etc.) the treated substrate (e.g.,coated substrate) retains equal to or at least about: 70%, 80%, 90%,95%, 99%, or 100% (or ranges including and/or spanning theaforementioned values) of its transmissivity under normal wearingconditions for a given period of time. In several embodiments, relativeto a untreated substrate, the transmissivity of the treated substrate isimproved by: 2.5%, 5.0%, 10%, 20%, 30%, 40%, or 50% (or ranges includingand/or spanning the aforementioned values) under equivalent normalwearing conditions for a given period of time. For instance, where atreated substrate is untreated substrate in substantially equivalentwear conditions (e.g., are placed side-by-side in a set of binoculars),after a given period of normal use, if the transmissivity of theuntreated substrate has decreased by 20% and the transmissivity of thetreated diamond has not decreased, this would be quantified as a 20%improvement in transmissivity for the treated substrate. In severalembodiments, the period of time after which transmissivity is measuredis a period of equal to or at least about: 1 week, 2 weeks, a month, 2months, 3 months, or ranges including and/or spanning the aforementionedvalues.

In several embodiments, advantageously, the coatings disclosed hereinmay be removed from the substrate using heat. For example, in severalembodiments, users may want to recover a diamond in its substantiallyoriginal form after coating. In several embodiments, users may want toreapply a fresh coating once the original coating has worn offpartially. In several embodiments, the coating removal process isperformed at a temperature equal to or at least about: 450° C., 500° C.,550° C., 600° C., or ranges including and/or spanning the aforementionedvalues. In several embodiments, the coating removal process is performedfor a period of time equal to or less than about: 30 minutes, 60minutes, 1.5 hours, 2.0 hours, 4 hours, 5 hours, 6 hours, or rangesincluding and/or spanning the aforementioned values. In severalembodiments, after removal, the coating can be refreshed using themethods disclosed elsewhere herein (plasma treatment, annealing,silanization, etc.).

In several embodiments, a diamond is a polished carbon crystal of anyweight, color, clarity, or cut. In several embodiments, the diamond is aslice. In several embodiments, the diamond is lab grown. In severalembodiments, the diamond is natural. In several embodiments, the diamondis a powder coating applied to a grinding wheel, silicon wafer, or otherflat or textured surface. In several embodiments, the diamond is aconstituent of a composite. In several embodiments, the diamond is ananoparticle. In several embodiments, the diamond contains defect sitesincluding nitrogen vacancy centers, silicon vacancy centers, borondoping, or other chemical or physical inclusion. Henceforth thesevariations of diamond are collectively referred to as “diamond”.

As disclosed elsewhere herein, in some embodiments, the gemstone isdiamond. In several embodiments, using S-units as disclosed herein,maintains the original look of the diamond (or other gemstone or othersubstrate). In several embodiments, the clarity and/or color of diamondis substantially unchanged after a molecular coating is applied. Forexample, in some embodiments, a diamond that has a color grade of D willremain a color grade of D after coating. In several embodiments, adiamond that has a clarity of VVS₂ will remain a clarity of VVS₂ aftercoating.

In several embodiments, a coating is applied to a diamond. In severalembodiments, the coating is a monolayer. In several embodiments,chemical agents are not used to form a sub-monolayer or pre-coatingprior to adding the monolayer on the diamond surface.

In several embodiments, as disclosed elsewhere herein, applying coatingsto an untreated diamond results in poor adhesion, so the diamond must bemodified in order to achieve suitable durability for a non-stick,self-cleaning, or lipophobic application. In several embodiments,chemical coatings will not attach to the surface of the diamond,chemically or physically, without an engineered modification of thediamond crystal interface. Some embodiments of such engineeredmodifications are disclosed herein. In several embodiments, theengineered modification includes functionalizing the diamond surfacewith an organic constituent. In several embodiments, the diamond surfacecomposition is changed to reflect the chemistry of an organicconstituent. In several embodiments, those chemical functionalitiesinclude molecules that form chemical bonds to other chemical entities(that normally would not react with a diamond surface). In severalembodiments, the added chemical functionalities include molecules thatform chemical bonds to specific surfaces or are generalized thatchemically connect to any surface. Such surface/molecule couplingreactions could be anything for which an appropriate connection isprepared. In several embodiments, these include “click-chemistry”molecular coupling (e.g., azide/alkyne pairs), molecular silanes (e.g.,R—Si(LG)₃) reacting with oxygen-containing chemical speciesfunctionality, carbenes reacting with carbon-hydrogen functionality, orsupramolecular interactions such as between a surface-bound adamantyl orcarborane group and a cyclodextrin molecule or modified-cyclodextrinmolecule. The nature of the organic component (e.g., R) can be anychemical functionality including aliphatic, aromatic carbon chains orother molecules, or themselves include functional groups for subsequentmodification.

Diamond is non-uniformly chemically functional, with a mixture ofsurface states consisting of an uncharacterized mixture of hydrogen,oxygen (hydroxyl, carboxyl), or various carbon-containing species. Oneor multiple of these species is not amenable to chemicalfunctionalization. An uncontrolled chemical interface preventsdeposition of well-controlled, durable, stable, and functional chemicalsurface coatings. One or more embodiments disclosed herein solve theseor other problems.

In several embodiments, diamond is pretreated with chemical and physicalmodification to transform one surface chemical identity into another. Inseveral embodiments, the diamond is treated to convert a larger fractionof the surface to hydrogen termination. In several embodiments, thediamond is pretreated to convert a larger fraction of the surface tooxygen containing species (e.g. hydroxyl, carboxyl).

In several embodiments, hydrogen surface termination ratio is increasedby application of hydrogen plasma in vacuum. In several embodiments, thehydrogen surface termination ratio is increased by polishing in thepresence of a hydrocarbon lubricant. In several embodiments, thehydrogen termination is functionalized using a carbene generated in situby elimination of diazomethane groups.

In several embodiments, the oxygen species (e.g., reactive oxygenspecies) surface ratio is increased by application of chemicaltreatment. In several embodiments, this chemical treatment is a mixtureof sulfuric acid and hydrogen peroxide. In several embodiments, thismixture of acid and peroxide cleans and removes adventitious species asa pretreatment of the diamond crystal and can remove a thin outermostdiamond layer. In several embodiments, this mixture of acid and peroxideincreases the ratio of oxygen-containing species at the diamond surface.In several embodiments, this ratio is measured by the water contactangle of a water droplet sitting on a diamond surface. In severalembodiments, higher proportions of oxygen species lead to a lower watercontact angle (e.g., <40°). Higher proportions of hydrogen or carbontermination will lead to a higher water contact angle (e.g., >40°, <80°)

In several embodiments, diamonds are treated (e.g., pretreated) with ahydrogen plasma. In several embodiments, plasma treatment renders thesurface rich in hydrogen species. In several embodiments, the surfacewill be temporarily highly hydrophilic but will return to WCA˜60° overseveral days. In several embodiments, hydrogen can be replaced withhydroxide by treatment of diamond surfaces in a furnace at >500° C.under wet nitrogen flow at ˜10 psi. In several embodiments, ahydrogen-rich surface will be converted to hydroxyl-rich or to othersimilar and related species.

In several embodiments, molecules containing silane or siloxanefunctional groups are used to modify diamond surfaces (e.g., silanizingagents, as disclosed elsewhere herein). In several embodiments, themolecules have trichlorosilane functional groups, or methoxy/ethoxyderivatives of the same. In several embodiments, the organic portion(e.g., “R”) of the molecule is optionally substituted alkyl. In someembodiments the organic portion of the molecule is a linear alkyl chainof variable length. In some embodiments the organic portion of themolecule is a branched alkyl chain of variable length. In someembodiments the organic portion of the molecule is a linear fluorocarbonchain. In some embodiments the organic portion of the molecule is abranched fluorocarbon chain. In some embodiments the molecule is dipodalwith multiple silane functional groups. In some embodiments chemicalreactions convert trichlorosilane groups to silanol, and then toalkyloxy groups. In some embodiments molecules contain alkylfunctionality. In several embodiments, chemicals (e.g., silane) areattached to untreated diamond. In several embodiments, chemicals areattached to treated diamond (e.g., pretreated with plasma as disclosedelsewhere herein). In several embodiments, chemicals are attached todiamond with an adhesion layer. In several embodiments, chemicals areattached to an applied or engraved texture. In several embodiments, anatomic layer deposition is performed on the hydroxyl or directlyfunctionalized by any species capable of reacting with surface hydroxylgroups. In several embodiments, the hydroxyl-rich surface is used toattach a secondary attachment layer.

In several embodiments, diamond surfaces are treated with chemicalagents to functionalize the diamond surface. In several embodiments, anadhesion layer rich in adhesion promoters is applied via atomic layerdeposition (ALD), Aluminum oxide (Al₂O₃) deposited using trimethylaluminum (TMA) and water, at 0.1-50 nm thickness to the oxygen-richdiamond. In several embodiments, ALD is used to deposit silicon dioxide,hafnia, metallic layers (e.g. copper, gold), or other ALD-compatiblematerial to the diamond surface.

In several embodiments, the ALD process can be used to impart color ortexture to the diamond surface. In several embodiments, the adhesionlayer coating can be used as the final coating. In several embodiments,texture can be engraved or etched using chemical or physical means. Inseveral embodiments, the adhesion layer coating can be furtherchemically functionalized. In several embodiments, the adhesion coatingcan be applied to the monolayer coating. In several embodiments, allcoatings can be applied in consecutive order forming multilayer stacks.

In several embodiments, the surface of a gemstone (e.g., diamond) afterchemically modification using a silane with a perfluorinated tail arehydrophobic. In several embodiments, the contact angle for water on thesurface of a silane-treated gemstone (e.g., silanized diamond having asilane with a perfluorinated tail) is greater than or equal to about:80°, 85°, 90°, 95°, 100°, 105°, 110°, 115°, 120°, 125°, 130°, or rangesincluding and/or spanning the aforementioned values. In severalembodiments, the contact angle for water on the treated (e.g., plasmatreated and silanized) gemstone is equal to or at least about 50%, 75%,90%, 95%, 99% greater than the contact angle for water on the gemstonebefore treatment (or ranges including and/or spanning the aforementionedvalues). In several embodiments, the contact angle for water on thetreated gemstone is changed relative to the contact angle for water onthe untreated gemstone by equal to or at least about: 30°, 35°, 40°,45°, 50°, 55°, 60°, 65°, 70°, 75°, 80°, 85°, 90°, 95°, 100°, 105°, 110°,115°, 120°, 125°, 130°, or ranges including and/or spanning theaforementioned values.

In several embodiments, the contact angle for water on a raw diamond(e.g., an untreated, cut diamond that has not been chemically modified)is equal to or at least about: 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°,80°, 90°, 95°, 100°, or ranges including and/or spanning theaforementioned values.

In several embodiments, the contact angle for water on a precursordiamond (e.g., a diamond that has been subject to plasma treatment butnot annealing) is equal to or at least about: 60°, 65°, 70°, 75°, 80°,85°, 90°, 95°, 100°, or ranges including and/or spanning theaforementioned values.

In several embodiments, the contact angle for water on a reactivegemstone (e.g., that has been plasma treated and water annealed) isequal to or at least about: 10°, 20°, 30°, 35°, 40°, 45°, 50°, 55°, 60°,65°, 70°, 75°, or ranges including and/or spanning the aforementionedvalues. In several embodiments, the contact angle for water on a plasmatreated and water annealed gemstone is equal to or at least about: 10°,20°, 30°, 35°, 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°, or rangesincluding and/or spanning the aforementioned values.

In several embodiments, surfaces chemically modified by fluorinatedcarbon chains are superhydrophobic with water contact angles >120°.Superhydrophobicity improves contamination release and anti-smudgecharacteristics while enhancing cleaning. In several embodiments,superhydrophobicity is caused by a chemical monolayer, multilayer, ormesh on diamond. In several embodiments, superhydrophobicity is causedby texturing on diamond. In several embodiments, superhydrophobicity iscaused by a combination of chemical monolayer, multilayer, mesh andtexturing on diamond.

In some embodiments replacing the fluorinated carbon chains withnon-fluorinated hydrocarbons eliminates fluorine-based waste. In severalembodiments, surfaces chemically modified with non-fluorinated carbonchains are hydrophobic with water contact angles >100°. Thehydrophobicity improves contamination release and anti-smudgecharacteristics while enhancing cleaning. In some embodimentsfluorinated chains are environmentally undesirable. In some embodimentsan alkyl-based hydrocarbon chain or aryl-based ring systems. In someembodiments the fluorinated chains are replaced with perchlorinatedcarbon chains.

EXAMPLES

Reagents and solvents were acquired from commercial sources withoutadditional purification. (Heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane was obtained from Gelest. A slotted two inch waferdipper was obtained from Shame Master. Diamonds were acquired from JeanDousset diamonds and were table diamond cut 3 mm stones. Water contactangle measurements were performed using a One Attension—ThetaGoniometer. Plasma treatment was performed using a Tergio table topplasma generator. An electric furnace was built in-house.

Example 1: Plasma Treatment and Water Vapor Annealing Procedure

Upon receipt, a new unprocessed diamond (e.g., a raw diamond) wasunpackaged. The raw diamond was placed within a fabricated, aluminumdiamond seat in the goniometer. The water contact angle was measuredusing the One Attension-Theta Goniometer from Biolin Scientific. Thedroplet size used for contact angle measurement was 0.75 μL, thoughsmaller droplets (0.5 μL) could also be used. The contact angle of waterfor the diamond was roughly 35°-50°. Upon positioning the diamond in thediamond seat, a water droplet was placed on the diamond. A photograph ofthe droplet on the diamond was taken.

At that time, the raw diamond was plasma treated to generate a precursordiamond surface. The raw diamond was placed in a quartz plasma chamberof the plasma generating device. The plasma chamber was evacuated. A gasflow of oxygen and/or hydrogen was used to generate the reactivesurface. The gas flow rate was set to 99 standard cubic centimeters perminute (sccm) for the desired gas. The pressure in the chamber wasadjusted to about 320 mtorr and the gas flow rate was adjusted to 0sccm. The plasma generating device is then operated to generate cleandiamond surface. Sample conditions include: High Pressure 02 plasma,direct, 150 W, 20 sccm, 2 min; 02 Plasma, remote, 100 W, 10 sccm, 15min; H₂ plasma, remote, 150 W, 20 sccm, 30 min. FIG. 5 provides anexemplary plasma treatment program (as does Step A of Scheme 1, FIGS. 2Aand 2B). The contact angle of the precursor diamond surface wasmeasured.

The plasma-cleaned diamond surface was then annealed using water. Toform OH terminated diamond surfaces, the CH-terminated diamond sampleswere subjected to water vapor (wet) annealing. As mentioned above, FIG.2B shows the plasma treatment of a raw diamond in Step A. After theprecursor diamond surface is generated through plasma treatment, thediamond surface is annealed using water. The annealing treatment (Step Bof FIG. 2B) was performed under an atmosphere of nitrogen bubbledthrough ultrapure water in a quartz tube in an electric furnace (asshown in FIG. 3 ). The annealing process is also shown in FIG. 5 (and inStep B of FIGS. 2A and 2B). The water saturated nitrogen is passedthrough the furnace at elevated temperatures (e.g., 300-700° C. for 1 hto 2 h). The flow of the nitrogen gas was 400 sccm. After annealing, areactive diamond surface results.

The water contact angle of the reactive diamond surface was measuredusing the One Attension-Theta Goniometer from Biolin Scientific. Thedroplet size used for contact angle measurement was 0.75 μL. Uponpositioning the reactive diamond in the diamond seat, a water dropletwas placed on the reactive diamond. A photograph of the droplet on thediamond was taken. The left panel of FIG. 4 shows a photograph of a dropof water on the reactive diamond surface. As shown, the contact angle ofthe water droplet is less than 45°, indicating a hydrophilic surface.

Example 2: Low Temperature Preparation of the Silanized Surface HavingAnti-Soiling Properties

To prepare a functionalized diamond surface the following procedureswere performed. A solution of isooctane and carbon tetrachloride wasprepared. Magnesium sulfate was added to dry the solution of any water.The dry solution was decanted away from the magnesium sulfate. The drysolution was covered and placed in a freezer to provide a chilledsolution. At that time, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane (FDTS) was added to the solution. The FDTS was allowedto mix in the organic solution for 10 minutes in the freezer. At thattime, the reactive diamond were dipped into the solution using a Teflondipper. The reactive diamond was submerged and the reaction solution wasplaced back in the freezer for at least 30 minutes. After 30 minutes,the diamond samples were removed from the freezer. The diamonds wereremoved from the solution and rinsed with ethanol. Other coatedsubstrates can be prepared using different substrates or differentsilanizing agents in view of these procedures.

The water contact angle of the functionalized diamond surface wasmeasured using the One Attension-Theta Goniometer from BiolinScientific. The droplet size used for contact angle measurement was 0.75μL. Upon positioning the functionalized diamond in the diamond seat, awater droplet was placed on the functionalized diamond. A photograph ofthe droplet on the diamond was taken. The right panel of FIG. 4 shows aphotograph of a drop of water on the functionalized diamond surface. Asshown, the contact angle of the water droplet is over 105°, indicating ahydrophobic surface.

Example 3: Desorption of the Silanized Surface Having Anti-SoilingProperties

Advantageously, the silanized monolayer coating of the diamond can beremoved (to afford the raw diamond) and/or regenerated. For instance, ifafter a period of time, the monolayer surface has degraded, it can beremoved completely and regenerated. To remove the monolayer, thediamonds are placed in a furnace at 550° C. for 0.5 hrs or 500° C. for 2hrs. Retreatment can then be performed using the procedures of Examples1 and 2.

Example 4: Abrasion Testing (Coating Durability)

To test the covalent coating's durability, the table surface of adiamond (3 mm in diameter) was rubbed against a cotton fabric along a 3cm length of the cloth. One abrasion cycle was equal to one round tripof rubbing the diamond with finger on the straight line of cotton cloth(6 total cm). The diamond was subject to 100 abrasion cycles, then anadditional 100 abrasion cycles (200 abrasion cycles total). Eachabrasion cycle used a constant pressure provided by a finger-tip. Afterthe first 100 abrasive cycles, the water contact angle after wasmeasured. The water contact angle after was measured after the total of200 cycles as well. Because one abrasion cycle covered a total of 6 cmdistance, this was equivalent to 20 individual rubs across the table(e.g., the top face) of the diamond. Thus, 20 abrasion cycles isequivalent to 20 round trips, or 400 times rubbing the entire surface ofthe table of the diamond. 200 abrasion cycles was equivalent to 10 ×20round trip or 4000 times of rubbing the entire table surface of thediamond. Assuming consumers average 10 times of rubbing exposure perday, then if coating survives 10×20 abrasion cycles, the coating isestimated to last 400 days, longer than 1 year. The contact angle ofwater after coating was approximately 1000 to 1150 contact angle aftercoating. The contact angle of water after 100 abrasion cycles wasapproximately 900 to 105°. The contact angle of water after 100 abrasioncycles was approximately 850 to 100°.

What is claimed is:
 1. A soil resistant diamond comprising: a jewelrygrade diamond gemstone having an anti-soiling surface coating, theanti-soiling surface coating comprising a monolayer, the diamond surfaceand monolayer being represented by Surface (I):

where n is an integer selected from 0, 1, 2, 3, or 4; m is an integerranging from 1 to 15; wherein the soil resistant diamond is prepared by:plasma treating a surface of a raw diamond to provide a precursordiamond having a precursor diamond surface, the precursor diamondsurface being chemically different than the surface of the raw diamond;annealing the precursor diamond to provide a reactive diamond having areactive diamond surface, the reactive diamond surface being differentfrom the precursor diamond surface; and exposing the reactive diamondsurface to a silanizing agent comprising an S-unit; wherein each“S-unit” is a silane unit consisting of Si(CH₂)_(n)(CF₂)_(m)CF₃.
 2. Thesoil resistant diamond of claim 1, wherein the surface of the rawdiamond comprises hydroxyl groups, carbonyl groups, carboxylic acidgroups, epoxide groups, C—H groups, and C—C groups, as represented inSurface (I-r) by groups A¹, A², A³, A⁴, A⁵, and A⁶, respectively:


3. The soil resistant diamond of claim 1 or 2, wherein a contact anglefor water on the surface of the raw diamond ranges from 50° to 80°. 4.The soil resistant diamond of any one of claims 1 to 3, wherein theprecursor diamond surface comprises a ratio of A¹ and A⁶ groups relativeto a total number of surface groups A¹ to A⁶ that is higher than a ratioof A¹ and A⁶ groups relative to a total number of surface groups A¹ toA⁶ for the raw diamond surface.
 5. The soil resistant diamond of any oneof claims 1 to 4, wherein a contact angle for water on the precursordiamond surface ranges from 400 to 80°.
 6. The soil resistant diamond ofany one of claims 1 to 5, wherein the reactive diamond surface comprisesa ratio of A¹ groups relative to a total number of surface groups A¹ toA⁶ that is higher than a ratio of A¹ groups relative to a total numberof surface groups A¹ to A⁶ for the precursor diamond surface.
 7. Thesoil resistant diamond of any one of claims 1 to 6, wherein a contactangle for water on the reactive diamond surface ranges from 10° to 40°8. The soil resistant diamond of any one of claims 1 to 6, wherein n is2.
 9. The soil resistant diamond of any one of claims 1 to 6, wherein nis
 2. 10. The soil resistant diamond of any one of claims 1 to 9,wherein m is between 6 and
 12. 11. The soil resistant diamond of any oneof claims 1 to 9, wherein m is
 8. 12. The soil resistant diamond of anyone of claims 1 to 11, wherein each nm² of the soil resistant diamondsurface comprises equal to or at least 2 S-units.
 13. The soil resistantdiamond of any one of claims 1 to 12, wherein the Surface (I) is furtherrepresented by Surface (I-i):


14. A soil resistant lens comprising: a lens having an anti-soilingsurface coating, the anti-soiling surface coating comprising amonolayer, the lens surface and monolayer being represented by Surface(I):

where n is an integer selected from 0, 1, 2, 3, or 4; m is an integerranging from 1 to 15; wherein the soil resistant lens is prepared by:plasma treating a surface of an untreated lens to provide a precursorlens having a precursor lens surface, the precursor lens surface beingchemically different than the surface of the untreated lens; annealingthe precursor lens to provide a reactive lens having a reactive lenssurface, the reactive lens surface being different from the precursorlens surface; and exposing the reactive lens surface to a silanizingagent comprising an S-unit; wherein each “S-unit” is a silane unitcomprising of Si(CH₂)_(n)(CF₂)_(m)CF₃.
 15. A molecularly coated surfacecomprising, Formula I:S-A

T)_(p)   Formula I where S represents a surface of a gemstone and-A(-T)_(p) represents the molecular coating; A is an silane or siloxanecovalently bonded to S; T is a pendant tail moiety bonded to A; p is aninteger between 1 and 5; and wherein the coated surface has differentphysical properties and/or chemical properties than the surface prior tocoating.
 16. The surface of claim 15, wherein T is an C₁-C₁₀ alkyl orC₁-C₁₀ perfluoroalkyl.
 17. The surface of claim 15 or 16, wherein T isselected from the group consisting of heptafluoroisopropoxypropyl,nonafluorohexyl, tridecafluorohexyl, trifluoromethyl, or combinationsthereof.
 18. The surface of any one of claims 15 to 17, wherein thesurface is that of a diamond.
 19. A method of preparing the surface ofany one of claims 15 to 18, comprising exposing the surface to a reagentselected from: heptafluoroisopropoxypropyltrichlorosilane,heptafluoroisopropoxypropyltrimethoxysilane,bis(nonafluorohexyldimethylsiloxy)methyl-silylethyldimethylchlorosilane,tridecafluoro-2-(tridecafluorohexyl)decyltrichlorosilane,heneicocyl-1,1,2,2-tetrahydrodecyltrichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)methyldichlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane,(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyldichlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane,(heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, orcombinations thereof.
 20. The method of claim 19, comprising exposingthe surface to plasma treatment prior to exposure to the reagent.
 21. Adiamond comprising the surface of any one of claims 1 to 17.